Porous Inorganic/Organic Hybrid Materials With Ordered Domains for Chromatographic Separations and Processes for Their Preparation

ABSTRACT

Porous hybrid inorganic/organic materials comprising ordered domains are disclosed. Methods of making the materials and use of the materials for chromatographic are also disclosed.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.60/592,971 filed Jul. 30, 2004, the entire contents of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION

Materials for chromatographic separations can be generally classified asinorganic (e.g., silica), organic (e.g., polydivinylbenzene), or hybridinorganic/organic materials.

As stationary phases for HPLC, organic-based materials are chemicallystable against strongly alkaline and strongly acidic mobile phases,allowing flexibility in the choice of mobile phase pH. However, organicchromatographic materials generally result in columns with lowefficiency, leading to inadequate separation performance, particularlywith low molecular-weight analytes. Furthermore, many organicchromatographic materials shrink and swell when the composition of themobile phase is changed. In addition, most organic chromatographicmaterials do not have the mechanical strength of typical chromatographicsilica.

Silica-based materials are mechanically strong and result in columnsthat do not show evidence of shrinking or swelling. However, limitedhydrolytic stability is a drawback with silica-based columns, becausesilica may be readily dissolved under alkaline conditions, generallypH >8.0, leading to the subsequent collapse of the chromatographic bed.Additionally, the bonded phase on a silica surface may be removed fromthe surface under acidic conditions, generally pH <2.0, and eluted offthe column by the mobile phase, causing loss of analyte retention.

Porous inorganic/organic hybrid materials have been introduced toovercome the above-mentioned deficiencies while attempting to maintainthe beneficial properties of purely organic and purely inorganicmaterials. These materials are synthesized from a mixture of inorganicand organofunctional silane monomers to prepare a copolymer, e.g.SiO₂/RSiO_(1.5) or SiO₂/R(SiO_(1.5))₂ and can be either particulate ormonolithic in form. See, e.g., K. Unger, J. Schick-Kalb, U.S. Pat. No.4,017,528; A. Sayari, S. Hamoudi, Chem. Mater. 13 (2001) 3151; K.Nakanishi, N. Soga, T. Minakuchi, U.S. Pat. No. 6,207,098; K. Nakanishi,N. Soga, Japanese patent application 2,893,104.

However, there is a number of problems with these materials when used inchromatographic separations. By and large, these problems arise becausethe particulate forms have been made by direct co-condensation of themonomers into a silicate form or via an intermediatepoly(organosiloxane) (POS). The resultant particles are commonlyirregular in shape, are not highly spherical, or have an irregularsurface morphology. Because of these irregularities in shape ormorphology, these particles do not afford the packing of highlyefficient columns that are required for good chromatography.

The particles further contain a large population of micropores with adiameter of about <40 Å. It is known that the diffusion of a molecule inthe pores of a material slows down measurably as the pore size becomessmaller than about 10 times the size of the analyte molecule, resultingin poor peak shape and band broadening. As a result, materials with alarge population of micropores are not particularly useful for mostchromatographic separations and have little utility.

In the case of monolithic materials, many of the monoliths lackmacropores that are required for low operating backpressures. Inmonolith cases where macropores have been achieved, the monolithscontain a large population of micropores with a diameter of about <40 Åand suffer the same disadvantages as described above. Hybrid materialscontaining only a small population of micropores and a sufficientpopulation of mesopores have been reported to solve this problem. See,e.g., Z. Jiang, R. Fisk, J. O'Gara, T. Walter, K. Wyndham U.S. Pat. No.6,686,035, and T. Walter, J. Ding, M. Kele, J. O'Gara, P. Iraneta WO03/014450.

However, the removal of the deleterious micropores is achieved by ahydrothermal treatment and comes at the expense of decreasing surfacearea, which consequently diminishes the material's retention capacity.In addition, the removal of the deleterious micropores results in aunimodal mesopore population that is polydisperse. Finally, all of thehybrid materials containing only a small population of micropores and asufficient population of mesopores are amorphous or disordered.

Thus, there is a need for hybrid materials having ordered domains, inwhich chromatographically desirable morphologies (e.g., sphericalparticles and monoliths with a bimodal pore size distribution ofmacropores and mesopores) are preserved. Although the analogouspreservation of purely inorganic silica gel particles has been reported,see, e.g., T. Martin, A. Galarneau, F. Di Renzo, F. Fajula, D. Plee,Angew. Chem. Int. Ed. 41 (2002) 2590, this has not yet been achieved forhybrid materials, especially those with a chromatographically-enhancingpore geometry. Therefore, porous inorganic/organic hybrid materialscomprising ordered domains and, advantageously, achromatographically-enhancing pore geometry are needed.

SUMMARY OF THE INVENTION

The present invention provides novel materials for chromatographicseparations, processes for their preparation, and separations devicescontaining the chromatographic materials. In particular, the inventionprovides porous inorganic/organic hybrid materials comprising ordereddomains and, in certain embodiments, chromatographically-enhancing poregeometries.

Thus, in one aspect the invention provides a porous hybridinorganic/organic material comprising ordered domains and having achromatographically-enhancing pore geometry.

In another aspect, the invention provides a porous hybridinorganic/organic material comprising ordered domains having formula I,II or III below:

(A)_(x)(B)_(y)(C)_(z)  (Formula I)

-   -   wherein the order of repeat units A, B, and C may be random,        block, or a combination of random and block;    -   A is an organic repeat unit which is covalently bonded to one or        more repeat units A or B via an organic bond;    -   B is an organosiloxane repeat unit which is bonded to one or        more repeat units B or C via an inorganic siloxane bond and        which may be further bonded to one or more repeat units A or B        via an organic bond;    -   C is an inorganic repeat unit which is bonded to one or more        repeat units B or C via an inorganic bond; and    -   x, y are positive numbers and z is a non negative number,        wherein    -   when z=0, then 0.002≦x/y≦210, and when z≠0, then    -   0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210;

(A)_(x)(B)_(y)(B*)_(y*)(C)_(z)  (Formula II)

-   -   wherein the order of repeat units A, B, B*, and C may be random,        block, or a combination of random and block;    -   A is an organic repeat unit which is covalently bonded to one or        more repeat units A or B via an organic bond;    -   B is an organosiloxane repeat units which is bonded to one or        more repeat units B or B* or C via an inorganic siloxane bond        and which may be further bonded to one or more repeat units A or        B via an organic bond;    -   B* is an organosiloxane repeat unit which is bonded to one or        more repeat units B or B* or C via an inorganic siloxane bond,        wherein B* is an organosiloxane repeat unit that does not have        reactive (i.e., polymerizable) organic components and may        further have a protected functional group that may be        deprotected after polymerization;    -   C is an inorganic repeat unit which is bonded to one or more        repeat units B or B* or C via an inorganic bond; and    -   x, y are positive numbers and z is a non negative number,        wherein    -   when z=0, then 0.002≦x/(y+y*)≦210, and when z≠0, then    -   0.0003≦(y+y*)/z≦500 and 0.002≦x/(y+y*+z)≦210; or

[A]_(y)[B]_(x)  (Formula III),

-   -   -   wherein x and y are whole number integers and A is

SiO₂/(R¹ _(p)R² _(q)SiO_(t))_(n) or SiO₂/[R³(R¹ _(r)SiO_(t))_(m)]_(n);

-   -   -   wherein R¹ and R² are independently a substituted or            unsubstituted C₁ to C₇ alkyl group, or a substituted or            unsubstituted aryl group, R³ is a substituted or            unsubstituted C₁ to C₇ alkylene, alkenylene, alkynylene, or            arylene group bridging two or more silicon atoms, p and q            are 0, 1, or 2, provided that p+q=1 or 2, and that when            p+q=1, t=1.5, and when p+q=2, t=1; r is 0 or 1, provided            that when r=0, t=1.5, and when r=1, t=1; m is an integer            greater than or equal to 2; and n is a number from 0.01 to            100;        -   B is:

SiO₂/(R⁴ _(v)SiO_(t))_(n)

-   -   -   wherein R⁴ is hydroxyl, fluorine, alkoxy, aryloxy,            substituted siloxane, protein, peptide, carbohydrate,            nucleic acid, or combinations thereof, R⁴ is not R¹, R², or            R³; v is 1 or 2, provided that when v=1, t=1.5, and when            v=2, t=1; and n is a number from 0.01 to 100;        -   wherein the material of formula III has an interior area and            an exterior surface, and said interior area of said material            has a composition represented by A; said exterior surface of            said material has a composition represented by A and B, and            wherein said exterior composition is between about 1 and            about 99% of the composition of B and the remainder            comprising A.

Another aspect of the invention provides a method of preparing theporous hybrid inorganic/organic materials provided by the invention. Themethod comprises the steps of:

-   -   (a) forming a pore restructuring template;    -   (b) restructuring the pores of a porous hybrid inorganic/organic        material by contacting the pores of the porous hybrid        inorganic/organic material with the pore restructuring template,        to thereby restructure the pores into ordered domains; and    -   (c) removing the pore restructuring template from the        restructured pores; to thereby prepare a porous hybrid        inorganic/organic material comprising ordered domains.

The invention also provides separations device comprising the poroushybrid inorganic/organic hybrid materials having ordered domainsprovided by the invention. In a related aspect, the invention provides achromatographic column comprising a column having a cylindrical interiorfor accepting a porous hybrid inorganic/organic material, and achromatographic bed comprising a porous hybrid inorganic/organicmaterial having ordered domains provided by the invention.

In another aspect, the invention provides porous hybridinorganic/organic materials having ordered domains, wherein thematerials are prepared by a method comprising the steps of:

-   -   (a) forming a pore restructuring template;    -   (b) restructuring the pores of a porous hybrid inorganic/organic        material by contacting the pores of the porous hybrid        inorganic/organic material with the pore restructuring template,        to thereby restructure the pores into ordered domains; and    -   (c) removing the pore restructuring template from the        restructured pores.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the formation of one type of pore restructuring template inthe form of a cylindrical micelle bundle of pore templating molecules(e.g., surfactant).

FIG. 2 shows particle pore transformation from amorphous to ordereddomain using the process of the invention.

FIG. 3 shows XRPD overlaid patterns displayed by hybrid materials 6r,6i, and 5e with ordered domains (full logarithmic scale) as measured byMethod A of Example 9.

FIG. 4 shows an XRPD pattern displayed by hybrid material 6t withordered domains (100% intensity scale) as measured by Method B ofExample 9.

FIG. 5 shows a transmission electron micrograph (TEM) of two materials:A (a hybrid material with ordered domains in accordance with theinvention) and B (an inorganic material with ordered domains).

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be more fully illustrated by reference to thedefinitions set forth below.

The term “hybrid”, i.e., as in “porous inorganic/organic hybridmaterials” includes inorganic-based structures wherein an organicfunctionality is integral to both the internal or “skeletal” inorganicstructure as well as the hybrid material surface. The inorganic portionof the hybrid material may be, e.g., alumina, silica, titanium orzirconium oxides, or ceramic material. In a preferred embodiment, theinorganic portion of the hybrid material is silica.

“Ordered domains” are those found in porous inorganic/organic hybridmaterials that exhibit diffraction peaks from about 0.8 to about 20°scan range (x-axis, 2θ units) as measured by X-ray powder diffraction(XRPD). XRPD is a well known characterization technique in the art (see,R. Jenkins, R. L. Snyder, Introduction to X-ray Powder Diffractometry,John Wiley & Sons, Inc., New York, © 1996). The 2θ position of theobserved diffraction peak maxima observed for porous inorganic/organichybrid materials with ordered domains excludes the diffraction peak atabout 20° to about 23° 2θ that results from atomic-range order and whichis observed and well known for amorphous materials. The percentage bymass of ordered domains within porous inorganic/organic hybrid materialsof the invention may be from 1-100%, where the balance of the mass isamorphous. Hybrid materials with ordered domains may be furthercharacterized by symmetry or space groups that are derived from XRPD,including but not limited to hexagonal (p6 mm), cubic (Ia3d), triclinic,monoclinic, orthorhombic, tetragonal, trigonal, and lamellar.

A “pore restructuring template” is defined as an agent that acts toorganize hybrid silicates to afford ordered domains within the hybridmaterial as the silicates dissolve and then precipitate duringhydrothermal treatment. A pore restructuring template is comprised ofone or more pore templating molecules and, optionally one or moretemplate swelling molecules.

A “pore templating molecule” is defined as a molecule which combineswith other pore templating molecules to form micelles, vesicles, ornetworks of a variety of shapes, sizes, symmetries and orders, e.g.cylindrical, spherical, hexagonal, cubic, triclinic, monoclinic,orthorhombic, tetragonal, trigonal, lamellar, unilamellar, planar,ellipsoidal, disk-like, rod-like, globule, worm-hole, inverted or otherhigher order networks. One or a combination of two or more poretemplating molecules can be used. The pore templating molecules areadvantageously used above their critical micelle concentrations (CMC)when the CMC exists. Pore templating molecules may be ionic ornon-ionic, and include a number of surfactants.

A “template swelling molecule” is defined as a molecule or group ofmolecules that act to swell a micelle, vesicle, or network of poretemplating molecules to a larger physical size.“Chromatographically-enhancing pore geometry” is found in hybridmaterials containing only a small population of micropores and asufficient population of mesopores. A small population of micropores isachieved in hybrid materials when all pores of a diameter of about <34 Åcontribute less than about 110 m²/g to the specific surface area of theparticle. Hybrid materials with such a low micropore surface area andwith a sufficient population of mesopores give chromatographicenhancements including high separation efficiency and good mass transferproperties (as evidenced by, e.g., reduced band spreading and good peakshape).

“Micropore surface area” is defined as the surface area in pores withdiameters less than or equal to 34 Å, determined by mulitpoint nitrogensorption analysis from the adsorption leg of the isotherm using the BJHmethod

A “sufficient population of mesopores” is achieved in hybrid materialswhen all pores of a diameter of about 35 Å to about 500 Å, e.g.,preferably about 60 Å to about 500 Å, e.g., even more preferably about100 Å to about 300 Å, sufficiently contribute to the specific surfacearea of the material, e.g., to about 35 to about 750 m²/g, e.g.,preferably about 65-550 m²/g, e.g., even more preferably about 100 to350 m²/g to the specific surface area of the material.

Porous inorganic/organic hybrid materials with ordered domains mayfurther be characterized by a unimodal or bimodal mesoporedistributions. A modal point is defined as the point where the porevolume is maximized (i.e., highest frequency) as a function of porediameter as determined from the dV/dlog(D) vs. D plot, as calculatedfrom the desorption leg of a nitrogen isotherm using the BJH method. Thematerials may still further be characterized by structural orientations,orders, or patterns at the molecular to atomic scale level as measuredby transmission electron microscopy (TEM).

A “unimodal mesopore distribution” is found where a single modal pointis observed between 35 and 500 Å.

A “bimodal mesopore distribution” is found in hybrid materials thatcontain two modal points in the plot of between 35 and 500 Å where onemodal point is located below 50 Å and the second is located above 50 Å.

The term “monolith” is intended to include a porous, three-dimensionalmaterial having a continuous interconnected pore structure in a singlepiece. A monolith is prepared, for example, by casting precursors into amold of a desired shape. The term monolith is meant to be distinguishedfrom a collection of individual particles packed into a bed formation,in which the end product comprises individual particles.

The terms “coalescing” and “coalesced” are intended to describe amaterial in which several individual components have become coherent toresult in one new component by an appropriate chemical or physicalprocess, e.g., heating. The term coalesced is meant to be distinguishedfrom a collection of individual particles in close physical proximity,e.g., in a bed formation, in which the end product comprises individualparticles.

The term “incubation” is intended to describe the time period during thepreparation of the inorganic/organic hybrid monolith material in whichthe precursors begin to gel.

The term “aging” is intended to describe the time period during thepreparation of the inorganic/organic hybrid monolith material in which asolid rod of monolithic material is formed.

The term “macropore” is intended to include pores of a material thatallow liquid to flow directly through the material with reducedresistance at chromatographically-useful flow rates. For example,macropores of the present invention are intended to include, but are notlimited to pores with a pore diameter larger than about 0.05 μm, poreswith a pore diameter ranging from about 0.05 μm to about 100 μm, poreswith a pore diameter ranging from about 0.11 μm to about 100 μm, andpores with a pore diameter ranging from about 0.5 μm to about 30 μm.

The term “chromatographically-useful flow rates” is intended to includeflow rates that one skilled in the art of chromatography would use inthe process of chromatography.

The term “functionalizing group” includes organic groups that impart acertain chromatographic functionality to a chromatographic stationaryphase, including, e.g., octadecyl (C₁₈) or phenyl. Such functionalizinggroups are present in, e.g., surface modifiers such as disclosed hereinwhich are attached to the base material, e.g., via derivatization orcoating and later crosslinking, imparting the chemical character of thesurface modifier to the base material. In an embodiment, such surfacemodifiers have the formula Z_(a)(R′)_(b)Si—R, where Z=Cl, Br, I, C₁-C₅alkoxy, dialkylamino, e.g., dimethylamino, or trifluoromethanesulfonate;a and b are each an integer from 0 to 3 provided that a+b=3; R′ is aC₁-C₆ straight, cyclic or branched alkyl group, and R is afunctionalizing group. R′ may be, e.g., methyl, ethyl, propyl,isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl orcyclohexyl; preferably, R′ is methyl.

The porous inorganic/organic hybrid particles and monolith materialswith or without ordered domains possess both organic groups and silanolgroups that may additionally be substituted or derivatized with asurface modifier. “Surface modifiers” include (typically) organic groupsthat impart a certain chromatographic functionality to a chromatographicstationary phase. Surface modifiers such as disclosed herein areattached to the base material, e.g., via derivatization or coating andlater crosslinking, imparting the chemical character of the surfacemodifier to the base material. In one embodiment, the organic groups ofthe hybrid materials react to form an organic covalent bond with asurface modifier. The modifiers can form an organic covalent bond to thematerial's organic group via a number of mechanisms well known inorganic and polymer chemistry including but not limited to nucleophilic,electrophilic, cycloaddition, free-radical, carbene, nitrene, andcarbocation reactions. Organic covalent bonds are defined to involve theformation of a covalent bond between the common elements of organicchemistry including but not limited to hydrogen, boron, carbon,nitrogen, oxygen, silicon, phosphorus, sulfur, and the halogens. Inaddition, carbon-silicon and carbon-oxygen-silicon bonds are defined asorganic covalent bonds, whereas silicon-oxygen-silicon bonds that arenot defined as organic covalent bonds. In general, the porousinorganic/organic hybrid particles and monolith materials can bemodified by an organic group surface modifier, a silanol group surfacemodifier, a polymeric coating surface modifier, and combinations of theaforementioned surface modifiers.

For example, silanol groups are surface modified with compounds havingthe formula Z_(a)(R′)_(b)Si—R, where Z=Cl, Br, I, C₁-C₅ alkoxy,dialkylamino, e.g., dimethylamino, or trifluoromethanesulfonate; a and bare each an integer from 0 to 3 provided that a+b=3; R′ is a C₁-C₆straight, cyclic or branched alkyl group, and R is a functionalizinggroup. R′ may be, e.g., methyl, ethyl, propyl, isopropyl, butyl,t-butyl, sec-butyl, pentyl, isopentyl, hexyl or cyclohexyl; preferably,R′ is methyl. In certain embodiments, the organic groups may besimilarly functionalized.

The functionalizing group R may include alkyl, aryl, cyano, amino, diol,nitro, cation or anion exchange groups, or embedded polarfunctionalities. Examples of suitable R functionalizing groups includeC₁-C₃₀ alkyl, including C₁-C₂₀, such as octyl (C₈), octadecyl (C₁₈), andtriacontyl (C₃₀); alkaryl, e.g., C₁-C₄-phenyl; cyanoalkyl groups, e.g.,cyanopropyl; diol groups, e.g., propyldiol; amino groups, e.g.,aminopropyl; and alkyl or aryl groups with embedded polarfunctionalities, e.g., carbamate functionalities such as disclosed inU.S. Pat. No. 5,374,755, the text of which is incorporated herein byreference. Such groups include those of the general formula

wherein l, m, o, r, and s are 0 or 1, n is 0, 1, 2 or 3 p is 0, 1, 2, 3or 4 and q is an integer from 0 to 19; R₃ is selected from the groupconsisting of hydrogen, alkyl, cyano and phenyl; and Z, R′, a and b aredefined as above. Preferably, the carbamate functionality has thegeneral structure indicated below:

wherein R⁵ may be, e.g., cyanoalkyl, t-butyl, butyl, octyl, dodecyl,tetradecyl, octadecyl, or benzyl. Advantageously, R⁵ is octyl, dodecyl,or octadecyl.

In a preferred embodiment, the surface modifier may be anorganotrihalosilane, such as octyltrichlorosilane oroctadecyltrichlorosilane. In an additional preferred embodiment, thesurface modifier may be a halopolyorganosilane, such asoctyldimethylchlorosilane or octadecyldimethylchlorosilane. In certainembodiments the surface modifier is octadecyltrimethoxysilane.

In another embodiment, the hybrid material's organic groups and silanolgroups are both surface modified or derivatized. In another embodiment,the hybrid materials are surface modified by coating with a polymer.

The term “aliphatic group” includes organic compounds characterized bystraight or branched chains, typically having between 1 and 22 carbonatoms. Aliphatic groups include alkyl groups, alkenyl groups and alkynylgroups. In complex structures, the chains can be branched orcross-linked. Alkyl groups include saturated hydrocarbons having one ormore carbon atoms, including straight-chain alkyl groups andbranched-chain alkyl groups. Such hydrocarbon moieties may besubstituted on one or more carbons with, for example, a halogen, ahydroxyl, a thiol, an amino, an alkoxy, an alkylcarboxy, an alkylthio,or a nitro group. Unless the number of carbons is otherwise specified,“lower aliphatic” as used herein means an aliphatic group, as definedabove (e.g., lower alkyl, lower alkenyl, lower alkynyl), but having fromone to six carbon atoms. Representative of such lower aliphatic groups,e.g., lower alkyl groups, are methyl, ethyl, n-propyl, isopropyl,2-chloropropyl, n-butyl, sec-butyl, 2-aminobutyl, isobutyl, tert-butyl,3-thiopentyl, and the like. As used herein, the term “nitro” means —NO₂;the term “halogen” designates —F, —Cl, —Br or —I; the term “thiol” meansSH; and the term “hydroxyl” means —OH. Thus, the term “alkylamino” asused herein means an alkyl group, as defined above, having an aminogroup attached thereto. Suitable alkylamino groups include groups having1 to about 12 carbon atoms, preferably from 1 to about 6 carbon atoms.The term “alkylthio” refers to an alkyl group, as defined above, havinga sulfhydryl group attached thereto. Suitable alkylthio groups includegroups having 1 to about 12 carbon atoms, preferably from 1 to about 6carbon atoms. The term “alkylcarboxyl” as used herein means an alkylgroup, as defined above, having a carboxyl group attached thereto. Theterm “alkoxy” as used herein means an alkyl group, as defined above,having an oxygen atom attached thereto. Representative alkoxy groupsinclude groups having 1 to about 12 carbon atoms, preferably 1 to about6 carbon atoms, e.g., methoxy, ethoxy, propoxy, tert-butoxy and thelike. The terms “alkenyl” and “alkynyl” refer to unsaturated aliphaticgroups analogous to alkyls, but which contain at least one double ortriple bond respectively. Suitable alkenyl and alkynyl groups includegroups having 2 to about 12 carbon atoms, preferably from 1 to about 6carbon atoms.

The term “alicyclic group” includes closed ring structures of three ormore carbon atoms. Alicyclic groups include cycloparaffins or naphtheneswhich are saturated cyclic hydrocarbons, cycloolefins which areunsaturated with two or more double bonds, and cycloacetylenes whichhave a triple bond. They do not include aromatic groups. Examples ofcycloparaffins include cyclopropane, cyclohexane, and cyclopentane.Examples of cycloolefins include cyclopentadiene and cyclooctatetraene.Alicyclic groups also include fused ring structures and substitutedalicyclic groups such as alkyl substituted alicyclic groups. In theinstance of the alicyclics such substituents can further comprise alower alkyl, a lower alkenyl, a lower alkoxy, a lower alkylthio, a loweralkylamino, a lower alkylcarboxyl, a nitro, a hydroxyl, —CF₃, —CN, orthe like.

The term “heterocyclic group” includes closed ring structures in whichone or more of the atoms in the ring is an element other than carbon,for example, nitrogen, sulfur, or oxygen. Heterocyclic groups can besaturated or unsaturated and heterocyclic groups such as pyrrole andfuran can have aromatic character. They include fused ring structuressuch as quinoline and isoquinoline. Other examples of heterocyclicgroups include pyridine and purine. Heterocyclic groups can also besubstituted at one or more constituent atoms with, for example, ahalogen, a lower alkyl, a lower alkenyl, a lower alkoxy, a loweralkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, ahydroxyl, —CF₃, —CN, or the like. Suitable heteroaromatic andheteroalicyclic groups generally will have 1 to 3 separate or fusedrings with 3 to about 8 members per ring and one or more N, O or Satoms, e.g. coumarinyl, quinolinyl, pyridyl, pyrazinyl, pyrimidyl,furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl,benzofuranyl, benzothiazolyl, tetrahydrofuranyl, tetrahydropyranyl,piperidinyl, morpholino and pyrrolidinyl.

The term “aromatic group” includes unsaturated cyclic hydrocarbonscontaining one or more rings. Aromatic groups include 5- and 6-memberedsingle-ring groups which may include from zero to four heteroatoms, forexample, benzene, pyrrole, furan, thiophene, imidazole, oxazole,thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazine andpyrimidine, and the like. The aromatic ring may be substituted at one ormore ring positions with, for example, a halogen, a lower alkyl, a loweralkenyl, a lower alkoxy, a lower alkylthio, a lower alkylamino, a loweralkylcarboxyl, a nitro, a hydroxyl, —CF₃, —CN, or the like.

The term “alkyl” includes saturated aliphatic groups, includingstraight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl(alicyclic) groups, alkyl substituted cycloalkyl groups, and cycloalkylsubstituted alkyl groups. In certain embodiments, a straight chain orbranched chain alkyl has 30 or fewer carbon atoms in its backbone, e.g.,C₁-C₃₀ for straight chain or C₃-C₃₀ for branched chain. In certainembodiments, a straight chain or branched chain alkyl has 20 or fewercarbon atoms in its backbone, e.g., C₁-C₂₀ for straight chain or C₃-C₂₀for branched chain, and more preferably 18 or fewer. Likewise, preferredcycloalkyls have from 4-10 carbon atoms in their ring structure, andmore preferably have 4-7 carbon atoms in the ring structure. The term“lower alkyl” refers to alkyl groups having from 1 to 6 carbons in thechain, and to cycloalkyls having from 3 to 6 carbons in the ringstructure.

Moreover, the term “alkyl” (including “lower alkyl”) as used throughoutthe specification and claims includes both “unsubstituted alkyls” and“substituted alkyls”, the latter of which refers to alkyl moietieshaving substituents replacing a hydrogen on one or more carbons of thehydrocarbon backbone. Such substituents can include, for example,halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy,aryloxycarbonyloxy, carboxylate, alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato,phosphinato, cyano, amino (including alkyl amino, dialkylamino,arylamino, diarylamino, and alkylarylamino), acylamino (includingalkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino,imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate,sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido,heterocyclyl, aralkyl, or an aromatic or heteroaromatic moiety. It willbe understood by those skilled in the art that the moieties substitutedon the hydrocarbon chain can themselves be substituted, if appropriate.Cycloalkyls can be further substituted, e.g., with the substituentsdescribed above. An “aralkyl” moiety is an alkyl substituted with anaryl, e.g., having 1 to 3 separate or fused rings and from 6 to about 18carbon ring atoms, e.g., phenylmethyl (benzyl).

The term “aryl” includes 5- and 6-membered single-ring aromatic groupsthat may include from zero to four heteroatoms, for example,unsubstituted or substituted benzene, pyrrole, furan, thiophene,imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine,pyridazine and pyrimidine, and the like. Aryl groups also includepolycyclic fused aromatic groups such as naphthyl, quinolyl, indolyl,and the like. The aromatic ring can be substituted at one or more ringpositions with such substituents, e.g., as described above for alkylgroups. Suitable aryl groups include unsubstituted and substitutedphenyl groups. The term “aryloxy” as used herein means an aryl group, asdefined above, having an oxygen atom attached thereto. The term“aralkoxy” as used herein means an aralkyl group, as defined above,having an oxygen atom attached thereto. Suitable aralkoxy groups have 1to 3 separate or fused rings and from 6 to about 18 carbon ring atoms,e.g., O-benzyl.

The term “amino,” as used herein, refers to an unsubstituted orsubstituted moiety of the formula —NR_(a)R_(b), in which R_(a) and R_(b)are each independently hydrogen, alkyl, aryl, or heterocyclyl, or R_(a)and R_(b), taken together with the nitrogen atom to which they areattached, form a cyclic moiety having from 3 to 8 atoms in the ring.Thus, the term “amino” includes cyclic amino moieties such aspiperidinyl or pyrrolidinyl groups, unless otherwise stated. An“amino-substituted amino group” refers to an amino group in which atleast one of R_(a) and R_(b), is further substituted with an aminogroup.

OVERVIEW OF THE INVENTION

The invention provides porous hybrid inorganic/organic materials havingordered domains. In certain embodiments, the hybrid materials alsopossess a chromatographically-enhancing pore geometry. The materials mayexist as spherical particles or monoliths.

The ordered domains of the materials are achieved by restructuring thepores of porous hybrid materials by hydrothermal treatment with a porerestructuring template. Chromatographically desirable morphologies(e.g., spherical particles and monoliths with a bimodal pore sizedistribution of macropores and mesopores) are preserved. In addition,materials can be further modified to enhance chromatographic properties.

The porous inorganic/organic hybrid materials with ordered domains and,advantageously, a chromatographically enhanced pore geometry, furtherhave high surface areas, which consequently enhance the materials'retention capacity. The materials may also have novel mechanical andchemical properties due to the pore ordering in comparison to anamorphous analog.

Porous Hybrid Inorganic/Organic Materials

The invention makes use of well-formed mesoporous materials. Suchmaterials are described in, e.g., U.S. Pat. No. 6,686,035, WO 03/014450A1, U.S. Pat. No. 6,528,167 and WO 04/041398.

Thus, in one embodiment, the pore restructuring process of the inventionprovides porous hybrid inorganic/organic materials comprising ordereddomains, wherein the materials generally have one of formula I, formulaII, or formula III as follows:

(A)_(x)(B)_(y)(C)_(z)  (Formula I)

-   -   wherein the order of repeat units A, B, and C may be random,        block, or a combination of random and block;    -   A is an organic repeat unit which is covalently bonded to one or        more repeat units A or B via an organic bond;    -   B is an organosiloxane repeat unit which is bonded to one or        more repeat units B or C via an inorganic siloxane bond and        which may be further bonded to one or more repeat units A or B        via an organic bond;    -   C is an inorganic repeat unit which is bonded to one or more        repeat units B or C via an inorganic bond; and    -   x, y are positive numbers and z is a non negative number,        wherein    -   when z=0, then 0.002≦x/y≦210, and when z≠0, then    -   0.0003≦y/z≦500 and 0.002≦x/(y+z)≦210;

(A)_(x)(B)_(y)(B*)_(y*)(C)_(z)  (Formula II)

-   -   wherein the order of repeat units A, B, B*, and C may be random,        block, or a combination of random and block;    -   A is an organic repeat unit which is covalently bonded to one or        more repeat units A or B via an organic bond;    -   B is an organosiloxane repeat units which is bonded to one or        more repeat units B or B* or C via an inorganic siloxane bond        and which may be further bonded to one or more repeat units A or        B via an organic bond;    -   B* is an organosiloxane repeat unit which is bonded to one or        more repeat units B or B* or C via an inorganic siloxane bond,        wherein B* is an organosiloxane repeat unit that does not have        reactive (i.e., polymerizable) organic components and may        further have a protected functional group that may be        deprotected after polymerization;    -   C is an inorganic repeat unit which is bonded to one or more        repeat units B or B* or C via an inorganic bond; and    -   x, y are positive numbers and z is a non negative number,        wherein    -   when z=0, then 0.002≦x/(y+y*)≦210, and when z≠0, then    -   0.0003≦(y+y*)/z≦500 and 0.002≦x/(y+y*+z)≦210; or

[A]_(y)[B]_(x)  (Formula III),

-   -   -   wherein x and y are whole number integers and A is

SiO₂/(R¹ _(p)R² _(q)SiO_(t))_(n) or SiO₂/[R³(R¹ _(r)SiO_(t))_(m)]_(n);

-   -   -   wherein R¹ and R² are independently a substituted or            unsubstituted C₁ to C₇ alkyl group, or a substituted or            unsubstituted aryl group, R³ is a substituted or            unsubstituted C₁ to C₇ alkylene, alkenylene, alkynylene, or            arylene group bridging two or more silicon atoms, p and q            are 0, 1, or 2, provided that p+q=1 or 2, and that when            p+q=1, t=1.5, and when p+q=2, t=1; r is 0 or 1, provided            that when r=0, t=1.5, and when r=1, t=1; m is an integer            greater than or equal to 2; and n is a number from 0.01 to            100;        -   B is:

SiO₂/(R⁴ _(v)SiO_(t))_(n)

-   -   -   wherein R⁴ is hydroxyl, fluorine, alkoxy, aryloxy,            substituted siloxane, protein, peptide, carbohydrate,            nucleic acid, or combinations thereof, R⁴ is not R¹, R², or            R³; v is 1 or 2, provided that when v=1, t=1.5, and when            v=2, t=1; and n is a number from 0.01 to 100;        -   wherein the material of formula III has an interior area and            an exterior surface, and the interior area of the material            has a composition represented by A; the exterior surface of            the material has a composition represented by A and B, and            wherein the exterior composition is between about 1 and            about 99% of the composition of B and the remainder            comprising A.

In one embodiment of the material of formula II, B is bonded to one ormore repeat units B or C via an inorganic siloxane bond and is bonded toone or more repeat units A or B via an organic bond.

In one embodiment of the material of Formula I or Formula II,0.003≦y/z≦50 and 0.02≦x/(y+z)≦21. In another embodiment, 0.03≦y/z≦5 and0.2≦x/(y+z)≦2.1.

In yet another embodiment of the material of Formula I or Formula II, Ais a substituted ethylene group, B is an oxysilyl-substituted alkylenegroup, and C is a oxysilyl group. In certain preferred embodiments, A isselected from the group consisting of

wherein each R is independently H or a C₁-C₁₀ alkyl group; m is aninteger of from 1 to 20; n is an integer of from 0 to 10; and Q ishydrogen, N(C₁₋₆alkyl)₃, N(C₁₋₆alkyl)₂(C₁₋₆alkylene-SO₃), orC(C₁₋₆hydroxyalkyl)₃. In certain embodiments, each R is independentlyhydrogen, methyl, ethyl, or propyl.

In certain embodiments of the materials of Formula I or Formula II, B isselected from the group consisting of

and wherein

-   -   B* is selected from a group consisting of

In certain embodiments of the materials of Formula I or Formula II, C is

In embodiments of the material of Formula III, the exterior surface hasa composition that is between about 50 and about 90% of composition B,with the remainder comprising composition A. In certain preferredembodiments, the surface has a composition that is between about 70 andabout 90% of composition B, with the remainder comprising composition A.

In various embodiments of the material of Formula III, R⁴ is hydroxyl;R⁴ is fluorine; R⁴ is methoxy; or R⁴ is

—OSi(R⁵)₂—R⁶

wherein R⁵ is a C₁ to C₆ straight, cyclic, or branched alkyl, aryl, oralkoxy group, a hydroxyl group, or a siloxane group, and R⁶ is a C₁ toC₃₆ straight, cyclic, or branched alkyl, aryl, or alkoxy group, whereinR⁶ is unsubstituted or substituted with one or more moieties selectedfrom the group consisting of halogen, cyano, amino, diol, nitro, ether,carbonyl, epoxide, sulfonyl, cation exchanger, anion exchanger,carbamate, amide, urea, peptide, protein, carbohydrate, nucleic acidfunctionalities, and combinations thereof. In certain embodiments, R⁶ isa C₁₈ group and in other embodiments, R⁶ is a cyanopropyl group.

The hybrid materials having formula I or formula II are prepared asdescribed in WO 04/041398, particularly Examples 1-9. In general, suchhybrid materials are prepared by the steps of (a) hydrolyticallycondensing an alkenyl-functionalized organosilane with atetraalkoxysilane, (b) copolymerizing the product of step (a) with anorganic olefin monomer, and (c) further hydrolytically condensing theproduct of step (b) to thereby prepare a porous inorganic/organichomogenous copolymeric hybrid material. In this embodiment, steps (b)and (c) may be performed substantially simultaneously. Steps (a) and (b)may be performed in the same reaction vessel.

Alternatively, the materials are prepared by the steps of (a)copolymerizing an organic olefin monomer with an alkenyl-functionalizedorganosilane, and (b) hydrolytically condensing the product of step (a)with a tetraalkoxysilane in the presence of a non-optically activeporogen to thereby prepare a porous inorganic/organic homogenouscopolymeric hybrid material. Steps (a) and (b) may be performed in thesame reaction vessel.

Also, the materials may be prepared by the steps of substantiallysimultaneously copolymerizing an organic monomer with analkenyl-functionalized organosilane and hydrolytically condensing saidalkenyl-functionalized organosilane with a tetraalkoxysilane to therebyprepare a porous inorganic/organic homogenous copolymeric hybridmaterial.

The copolymerizing step of the foregoing methods may be freeradical-initiated and the hydrolytically condensing step of theforegoing methods may by acid- or base-catalyzed. Additionally, thereaction may be heated following the addition of the free radicalpolymerization initiator. A porogen may be used.

Hybrid materials of Formula III above are prepared as described in U.S.Pat. No. 6,528,167, in particular Examples 1-12. In general, thematerials are prepared by a five-step process. In the first step, anorganotrialkoxysilane such as methyltriethoxysilane, and atetraalkoxysilane such as tetraethoxysilane (TEOS) are prepolymerized toform polyalkylalkoxysiloxane (PAS) by co-hydrolyzing a mixture of thetwo components in the presence of an acid catalyst. In the second step,the PAS is suspended in an aqueous medium in the presence of asurfactant and gelled into porous spherical particles of hybrid silicausing a base catalyst. In the third step, the pore structure of thehybrid silica particles is modified by hydrothermal treatment, producingan intermediate hybrid silica product which may be used for particularpurposes itself, or desirably may be further processed below. The abovethree steps of the process allow much better control of the particlemorphology, pore volume and pore sizes than those described in the priorart, and thus provide the chromatographically-enhancing pore geometry.In a fourth step, one or more of the surface organo groups such as themethyl group are replaced with a hydroxyl, fluorine, alkoxy, or aryloxygroup.

In the fifth step, the original and newly formed surface silanol groupsof the hybrid silica may be further derivatized with organic functionalgroups, such as by reacting with a halopolyorganosilane such asoctadecyldimethylchlorosilane. The surface coverage of the organo groupssuch as octadecyl groups is higher than in conventional hybrid-basedpacking materials, and subsequently the derivatized materials may haveincreased stability in low pH mobile phases.

In another embodiment, the invention provides porous hybridinorganic/organic materials comprising ordered domains and having achromatographically-enhancing pore geometry. Such materials aredescribed in U.S. Pat. No. 6,686,035 and WO 03/014450 and have theformula SiO₂/(R² _(p)R⁴ _(q)SiO_(t))_(n) or SiO₂/[R⁶(R²_(r)SiO_(t))_(m)]_(n) wherein R² and R⁴ are independently C₁-C₁₈aliphatic or aromatic moieties (which may additionally be substitutedwith alkyl, aryl, cyano, amino, hydroxyl, diol, nitro, ester, ionexchange or embedded polar functionalities), R⁶ is a substituted orunsubstituted C₁-C₁₈ alkylene, alkenylene, alkynylene or arylene moietybridging two or more silicon atoms, p and q are 0, 1 or 2, provided thatp+q=1 or 2, and that when p+q=1, t=1.5, and when p+q=2, t=1; r is 0 or1, provided that when r=0, t=1.5, and when r=1, t=1; m is an integergreater than or equal to 2, and n is a number from 0.03 to 1.5, morepreferably, 0.1 to 1, and even more preferably 0.2 to 0.5. R² may beadditionally substituted with a functionalizing group R (defined above).In one embodiment, n is a number from 0.03 to 1.5. In a preferredembodiment, n is a number from 0.2 to 0.5.

Porous inorganic/organic hybrid materials having ordered domainsgenerally have a specific surface area, as measured by N₂ sorptionanalysis, of about 50 to 800 m²/g, preferably about 100 to 700 m²/g,more preferably about 300 to 600 m²/g. The specific pore volume of thehybrid materials is generally about 0.25 to 1.5 cm³/g, preferably about0.4 to 1.4 cm³/g, more preferably about 0.7 to 1.3 cm³/g. The averagepore diameter of the materials is generally about 50 to 500 Å,preferably about 50 to 400 Å, more preferably about 50 to 300 Å. Porousinorganic/organic hybrid materials having ordered domains and alsohaving a chromatographically-enhancing pore geometry have a microporesurface area less than about 110 m²/g, preferably less than about 105m²/g, more preferably less than about 80 m²/g, and still more preferablyless than about 50 m²/g.

Porous inorganic/organic hybrid materials having pore ordered domainsand chromatographically-enhancing pore geometry may be made as describedbelow and in the specific instances illustrated in the Examples. In oneembodiment, the porous inorganic/organic hybrid materials having poreordered domains and chromatographically-enhancing pore geometry compriseporous spherical particles of hybrid silica.

Porous spherical particles of hybrid silica are prepared as described inU.S. Pat. No. 6,686,035. For example, porous spherical particles ofhybrid silica may, in a preferred embodiment, be prepared by amulti-step process. In the first step, one or more organoalkoxysilanessuch as methyltriethoxysilane, and a tetraalkoxysilane such astetraethoxysilane (TEOS) are prepolymerized to form apolyorganoalkoxysiloxane (POS), e.g., polyalkylalkoxysiloxane, byco-hydrolyzing a mixture of the two or more components in the presenceof an acid catalyst. In the second step, the POS is suspended in anaqueous medium in the presence of a surfactant or a combination ofsurfactants and gelled into porous spherical particles of hybrid silicausing a base catalyst. In the third step, the pore structure of thehybrid silica particles is modified by hydrothermal treatment, producingan intermediate hybrid silica product which may be used for particularpurposes itself, or desirably may be further processed below. The abovethree steps of the process allow much better control of the particlesphericity, morphology, pore volume and pore sizes than those describedin the prior art, and thus provide the chromatographically-enhancingpore geometry.

In one embodiment, the surface organic groups of the hybrid silica arederivatized or modified in a subsequent step via formation of an organiccovalent bond between the particle's organic group and the modifyingreagent. Alternatively, the surface silanol groups of the hybrid silicaare derivatized or modified into siloxane functional groups, such as byreacting with an organotrihalosilane, e.g., octadecyltrichlorosilane, ora halopolyorganosilane, e.g., octadecyldimethylchlorosilane.

Alternatively, the surface organic and silanol groups of the hybridsilica are both derivatized or modified. The surface of thethus-prepared material is then covered by the organic groups, e.g.,alkyl, embedded during the gelation and the organic groups added duringthe derivatization process or processes. The surface coverage by theoverall organic groups is higher than in conventional silica-basedpacking materials, and therefore the surface concentration of theremaining silanol groups in the hybrid silica is smaller.

Where the prepolymerization step involves co-hydrolyzing a mixture ofthe two or more components in the presence of an acid catalyst, thecontent of the organoalkoxysilane, e.g., organotrialkoxysilane can bevaried, e.g., from about 0.03 to about 1.5 mole per mole, or morepreferably, about 0.2 to about 0.5 mole per mole, of thetetraalkoxysilane. The amount of the water used for the hydrolysis canbe varied, e.g., from 1.10 to 1.35 mole per mole of the silane. Thesilane, water and the ethanol mixture, in the form of a homogeneoussolution, is stirred and heated to reflux under a flow of argon. Afterit is refluxed for a time sufficient to prepolymerize to formpolyorganoalkoxysiloxane (POS), e.g., polyalkylalkoxysiloxane, thesolvent and the side product, mainly ethanol, is distilled off from thereaction mixture. Thereafter, the residue is heated at an elevatedtemperature, e.g., in the range of 120 to 140° C. under an atmosphere ofargon for a period of time, e.g., 1.5 to 16 h. The residue is furtherheated at this temperature, e.g., for 1 to 3 h under reduced pressure,e.g., 10⁻²-10⁻³ torr, to remove any volatile species.

In the second step, the POS is suspended into fine beads in a solutioncontaining water and ethanol at 55° C. by agitation. The volume percentof ethanol in the solution is varied from 10 to 20%. A non-ionicsurfactant such as Triton X-100 or Triton X-45 is added into thesuspension as the suspending agent. Alternatively a mixture of TritonX-45 and low levels of glycolic acid ethoxylate 4-tert-butylphenylether, sodium dodecyl sulfate (SDS) or tris(hydroxymethyl)aminomethanelauryl sulfate (TDS) is added into the suspension as the suspendingagent.

The surfactants, e.g., alkylphenoxypolyethoxyethanol, are believed to beable to orient at the hydrophobic/hydrophilic interface between the POSbeads and the aqueous phase to stabilize the POS beads. The surfactantsare also believed to enhance the concentration of water and the basecatalyst on the surface of the POS beads during the gelation step,through their hydrophilic groups, which induces the gelling of the POSbeads from the surface towards the center. Use of surfactants tomodulate the surface structure of the POS beads stabilizes the shape ofthe POS beads throughout the gelling process, and minimizes orsuppresses formation of particles having an irregular shapes, e.g.,“shell shaped”, and inhomogeneous morphology.

It is also possible to suspend a solution containing POS and toluene inthe aqueous phase, instead of POS alone. The toluene, which is insolublein the aqueous phase, remains in the POS beads during the gelation stepand functions as a porogen. By controlling the relative amount oftoluene in the POS/toluene solution, the pore volume of the final hybridsilica can be more precisely controlled. This allows the preparation ofhybrid silica particles having large pore volume, e.g., 0.7-1.3 cm³/g.

The gelation step is initiated by adding the basic catalyst, e.g.,ammonium hydroxide into the POS suspension agitated at 55° C.Thereafter, the reaction mixture is agitated at the same temperature todrive the reaction to completion. Ammonium hydroxide is preferredbecause bases such as sodium hydroxide are a source of unwanted cations,and ammonium hydroxide is easier to remove in the washing step. Thethus-prepared hybrid silica is filtered and washed with water andmethanol free of ammonium ions, then dried.

Another embodiment of the invention provides porous inorganic/organichybrid monolith materials. Monolith materials are described, e.g., in WO03/014450 and in WO 04/041389. The hybrid monolith materials of theinvention may be indirectly prepared by coalescing the inorganic/organichybrid particles prepared as described above, or may be directlyprepared from inorganic and organic precursors. The hybrid monolithmaterials of the invention have a high surface coverage of organicgroups and, in certain embodiments, a chromatographically-enhancing poregeometry. Furthermore, by incorporation of the organic moieties in thesilica backbone, the hydrophobic properties of the hybrid monolithmaterial, as is seen in the hybrid particles of the invention, can betailored to impart significantly improved alkaline stability.

Porous inorganic/organic hybrid monolith materials may be made asdescribed below. In a preferred embodiment, the porous sphericalparticles of hybrid silica of the invention may be used as prepared bythe process noted above, without further modification. These hybridparticles are mixed with a second material, e.g., unbonded silica, andpacked into a container, e.g., a column. After packing is complete, themixture is coalesced, e.g., sintered, and the second material issubsequently removed by a washing step. The hybrid monolith material isfurther processed, e.g., rinsed with a solvent, to result in the hybridmonolith material.

Alternatively, the monolith material may be prepared directly by asol-gel process. The general process for directly preparing aninorganic/organic hybrid monolith material in a single step frominorganic and organic precursors can be characterized by the followingprocess.

First, a solution is prepared containing an aqueous acid, e.g., acetic,with a surfactant, an inorganic precursor, e.g., a tetraalkoxysilane,and an organic precursor, e.g., a organoalkoxysilane, e.g.,organotrialkoxysilane. The range of acid concentration is from about 0.1mM to 500 mM, more preferably from about 10 mM to 150 mM, and still morepreferably from about 50 mM to 120 mM. The range of surfactantconcentration is between about 3% and 15% by weight, more preferablybetween about 7 and 12% by weight, and still more preferably betweenabout 8% to 10% by weight. Furthermore, the range of the total silaneconcentration, e.g., methyltrimethoxysilane and tetramethoxysilane,employed in the process is kept below about 5 g/mL, more preferablybelow 2 g/mL, and still more preferably below 1 g/mL.

The sol solution is then incubated at a controlled temperature,resulting in a three-dimensional gel having a continuous, interconnectedpore structure. The incubation temperature range is between about thefreezing point of the solution and 90° C., more preferably between about20° C. and 70° C., still more preferably between about 35° C. and 60° C.The gel is aged at a controlled pH, preferably about pH 2-3, andtemperature, preferably about 20-70° C., more preferably about 35 to 60°C., for about 5 hours to about 10 days, more preferably from about 10hours to about 7 days, and still more preferably from about 2 days toabout 5 days, to yield a solid monolith material.

In order to further gel the hybrid material and to remove surfactant,the monolith material is rinsed with an aqueous basic solution, e.g.,ammonium hydroxide, at an temperature of about 0° C. to 80° C., morepreferably between about 20° C. and 70° C., and still more preferablybetween about 40° C. and 60° C. Additionally, in certain embodiments,the concentration of base is between about 10⁻⁵ N and 1 N, morepreferably between about 10⁻⁴ N and 0.5 N, and still more preferablybetween about 10⁻³ N and 0.1 N. The monolith material is rinsed forabout 1 to 6 days, more preferably for about 1.5 to 4.5 days, the stillmore preferably for about 2 to 3 days.

In addition, the monolith material may undergo hydrothermal treatment ina basic solution at an elevated temperature, e.g., in an autoclave, toimprove the monolith material's pore structure. The preferred pH of thehydrothermal treatment is between about 7.0 and 12.0, more preferablybetween about 7.3 and 11.0, and still more preferably between about 7.5and 10.6. The temperature of the hydrothermal treatment is between about110° C. and 180° C., more preferably between about 120° C. and 160° C.,and still more preferably between about 130° C. and 155° C. The monolithmaterial is then rinsed with water followed by a solvent exchange withmethanol, ethanol, acetonitrile, tetrahydrofuran, or hexane, and roomtemperature drying. The monolith material is then dried at about 70 to120° C., and preferably at about 100° C. under vacuum for about 16-24hours.

In a subsequent step, the surface organic groups of the hybrid monolithmaterial, prepared directly or indirectly, are optionally derivatized ormodified via formation of a covalent bond between the monolithmaterial's organic and/or silanol group and the modifying reagent,optionally including coating with a polymer, as is described for thehybrid particles.

The as-prepared hybrid materials of the invention can be modified in avariety of ways to enhance their chromatographic performance. In oneembodiment, the pore structure of the as-prepared hybrid material ismodified by hydrothermal treatment, which enlarges the openings of thepores as well as the pore diameters, as confirmed by nitrogen (N₂)sorption analysis, thereby providing a hybrid material with achromatographically-enhancing pore geometry. The hydrothermal treatmentis performed by preparing a slurry containing the as-prepared hybridmaterial and a solution of organic base in water, heating the slurry inan autoclave at an elevated temperature, e.g., about 143 to 168° C., fora period of about 6 to 28 h. The pH of the slurry can be adjusted to bein the range of about 8.0 to 10.7 using concentrated acetic acid. Theconcentration of the slurry is in the range of about 1 g hybrid materialper 5 to 10 mL of the base solution. The thus-treated hybrid material isfiltered, and washed with water until the pH of the filtrate reachesabout 7, washed with acetone, then dried at about 100° C. under reducedpressure for about 16 h. The resultant hybrid materials show averagepore diameters in the range of about 100-300 Å. The pores of thehydrothermally treated hybrid material may be restructured in a similarfashion to that of the hybrid material that is not modified byhydrothermal treatment as described in the present invention.

Moreover, the surface of the hydrothermally treated hybrid silicacontains organic groups, which can be derivatized by reacting with areagent that is reactive towards the hybrid materials' organic group.For example, vinyl groups on the material can be reacted with a varietyof olefin reactive reagents such as bromine (Br₂), hydrogen (H₂), freeradicals, propagating polymer radical centers, dienes, and the like. Inanother example, hydroxyl groups on the material can be reacted with avariety of alcohol reactive reagents such as isocyanates, carboxylicacids, carboxylic acid chlorides, and reactive organosilanes asdescribed below. Reactions of this type are well known in theliterature, see, e.g., March, J. “Advanced Organic Chemistry,” 3^(rd)Edition, Wiley, New York, 1985; Odian, G. “The Principles ofPolymerization,” 2^(nd) Edition, Wiley, New York, 1981; the texts ofwhich are incorporated herein by reference.

In addition, the surface of the hydrothermally treated hybrid silicaalso contains silanol groups, which can be derivatized by reacting witha reactive organosilane. The surface derivatization of the hybrid silicais conducted according to standard methods, for example by reaction withoctadecyltrichlorosilane or octadecyldimethylchlorosilane in an organicsolvent under reflux conditions. An organic solvent such as toluene istypically used for this reaction. An organic base such as pyridine orimidazole is added to the reaction mixture to catalyze the reaction. Theproduct of this reaction is then washed with water, toluene and acetoneand dried at about 80° C. to 100° C. under reduced pressure for about 16h. The resultant hybrid silica can be further reacted with a short-chainsilane such as trimethylchlorosilane or hexamethyldisilazane to endcapthe remaining silanol groups, by using a similar procedure describedabove.

More generally, the surface of the hybrid silica materials may besurface modified with a surface modifier, e.g., Z_(a)(R′)_(b)Si—R, whereZ=Cl, Br, I, C₁-C₅ alkoxy, dialkylamino, e.g., dimethylamino, ortrifluoromethanesulfonate; a and b are each an integer from 0 to 3provided that a+b=3; R′ is a C₁-C₆ straight, cyclic or branched alkylgroup, and R is a functionalizing group. R′ may be, e.g., methyl, ethyl,propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexylor cyclohexyl; preferably, R′ is methyl. The functionalizing group R mayinclude alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, cationor anion exchange groups, or alkyl or aryl groups with embedded polarfunctionalities. Examples of suitable R functionalizing groups includeC₁-C₃₀ alkyl, including C₁-C₂₀, such as octyl (C₈), octadecyl (C₁₈), andtriacontyl (C₃₀); alkaryl, e.g., C₁-C₄-phenyl; cyanoalkyl groups, e.g.,cyanopropyl; diol groups, e.g., propyldiol; amino groups, e.g.,aminopropyl; and alkyl or aryl groups with embedded polarfunctionalities, e.g., carbamate functionalities such as disclosed inU.S. Pat. No. 5,374,755, the text of which is incorporated herein byreference and as detailed hereinabove. In a preferred embodiment, thesurface modifier may be an organotrihalosilane, such asoctyltrichlorosilane or octadecyltrichlorosilane. In an additionalpreferred embodiment, the surface modifier may be ahalopolyorganosilane, such as octyldimethylchlorosilane oroctadecyldimethylchlorosilane. Advantageously, R is octyl or octadecyl.

The surface of the hybrid silica materials may also be surface modifiedby coating with a polymer. Polymer coatings are known in the literatureand may be provided generally by polymerization or polycondensation ofphysisorbed monomers onto the surface without chemical bonding of thepolymer layer to the support (type I), polymerization orpolycondensation of physisorbed monomers onto the surface with chemicalbonding of the polymer layer to the support (type II), immobilization ofphysisorbed prepolymers to the support (type III), and chemisorption ofpresynthesized polymers onto the surface of the support (type IV). see,e.g., Hanson et al., J. Chromat. A656 (1993) 369-380, the text of whichis incorporated herein by reference. As noted above, coating the hybridmaterial with a polymer may be used in conjunction with various surfacemodifications described in the invention. In a preferred embodiment,Sylgard® is used as the polymer. The pores of the surface modifiedhybrid materials may be restructured in a similar fashion to that of thehybrid material that is not modified by hydrothermal treatment asdescribed in accordance with the present invention.

Pore Restructuring to Provide Ordered Domains

The porous inorganic/organic hybrid materials, prepared as describedabove, are further processed to provide materials with ordered domains.Ordered domains are produced in these mesoporous hybrid materials bybase-catalyzed transformation. In accordance with the process, a varietyof pore templating molecules, optionally in combination with templateswelling molecules, can be used to form pore restructuring templates,with a variety of mesoporous hybrid materials. The process of theinvention makes use of mesopore restructuring protocols (e.g., poretemplating molecule choice, solution composition, template swellingmolecule choice, temperature and time) that have been used for therestructuring of porous inorganic materials (i.e. silica gel). (T.Martin, A. Galarneau, F. Di Renzo, F. Fajula, D. Plee, Angew. Chem. Int.Ed. 41 (2002) 2590.)

Although similar uniform pore networks (“ordered domains”) have beenreported (M. Grün, K. K. Unger, A. Matsumoto, K. Tsutsumi, Microporousand Mesoporous Materials 27 (1999) 207; A. Firouzi, D. Kumar, L. M.Bull, T. Besier, P. Sieger, Q. Huo, S. A. Walker, J. A. Zasadzinski, C.Glinka, J. Nicol, D. Margolese, G. D. Stucky, B. F. Chmelka, Science,267 (1995) 1138; M. Etienne, B. Lebeau, A. Walcarius, New. J. Chem. 26(2002) 384) for directly synthesized hexagonal (e.g., MCM-41), cubic(e.g., MCM-48) and lamellar (e.g., MCM-50) materials withoutchromatographically enhanced pore geometries, the pore restructuringprocess according to the invention differs from these processes in thatthe hybrid matrix is not prepared directly from siloxane monomers orsmall particle units (e.g., silica sols or tetraethoxysilane) but ratherfrom well-formed mesoporous hybrid materials, such as those describedabove.

The process of the invention is advantageous because it does notsignificantly alter the morphology of the hybrid materials. For example,when highly spherical hybrid materials (d_(p)=5 μm) are used in theprocess of the invention, the pore transformed product is comprised ofspherical materials with a particle size close to that of the startingmaterials (i.e., 5 μm). Materials, including both spherical andnon-spherical particles, produced in accordance with the process of theinvention can be prepared in sizes ranging from about 0.1 to about 60μm.

By controlling the reaction conditions (e.g., pore templating moleculechoice, solution composition, template swelling molecule choice,temperature and time), the pore profiles of the porous hybrid materialsproduced in accordance with the invention can be manipulated. Materialsprepared in accordance with the invention have high specific surfaceareas and have greatly reduced microporosity as compared to materialspresently used in high performance chromatographic applications. Theyfurther have crystalline domains or regions.

In accordance with the pore restructuring process of the invention, aporous hybrid inorganic/organic material comprising ordered domains isprepared by

-   -   (a) forming a pore restructuring template comprising a pore        templating molecule;    -   (b) restructuring the pores of a porous hybrid inorganic/organic        material by contacting the pores of the porous hybrid        inorganic/organic material with the pore restructuring template,        to thereby restructure the pores into ordered domains; and    -   (c) removing the template from the restructured pores; to        thereby prepare a porous hybrid inorganic/organic material        comprising ordered domains.

In one embodiment, the restructuring template is formed by using thetemplating molecule at a concentration above its critical micelleconcentration (CMC), optionally in combination with a template swellingmolecule. This results in the formation of micelles, vesicles, ornetworks of a variety of shapes, sizes and orders, of the poretemplating molecule, e.g., hexagonally close packed networks, as shownin FIG. 1.

Pore templating molecules may be ionic or non-ionic, and include anumber of surfactants. Examples of non-ionic pore templating moleculesinclude but are not limited to polymers and block copolymers, e.g.poly(ethyleneoxide)-poly(propyleneoxide)-poly(ethyleneoxide), e.g.,Pluronic® P123, Pluronic® P64, Pluronic P105, poly(ethyleneoxide)-alkylethers, e.g., Brij® 76, Brij® 30, Tween®, Span®, Triton®, Ipagel®. Ionicpore templating molecules include but are not limited to cationic,anionic, and zwitterionic molecules. The ionic pore templating moleculesmay further be divalent or multivalent as well as be amphiphilic orgemini in structure. Examples of ionic pore templating molecules includesodium bis(2-ethylhexyl)sulfosuccinate, glycolic acid ethoxylate4-tert-butylphenyl ether, glycolic acid ethoxylate lauryl ether,glycolic acid ethoxylate 4-nonylphenyl ether, glycolic acid ethoxylateoctyl ether, glycolic acid ethoxylate oleyl ether, sodium dodecylsulfate (SDS) or tris(hydroxymethyl)aminomethane lauryl sulfate (TDS),ammonium lauryl sulfate, alkyltrimethylammonium halides, e.g.,cetyltrimethylammonium chloride, cetyltrimethylammonium bromide,trimethylstearylammonium chloride. One or a combination of two or morepore templating molecules can be used. The pore templating molecules areadvantageously used above their critical micelle concentrations (CMC)when the CMC exists.

Template swelling molecules include, e.g., benzene, toluene,cyclohexane, cyclohexanol, dodecanol, chlorododecane,1,3,5-trimethylbenzene, and 1,3,5-triisopropylbenzene. In preferredembodiments, the template swelling molecule is 1,3,5-trimethylbenzene or1,3,5-triisopropylbenzene.

The pores of the porous hybrid inorganic/organic material arerestructured by contacting the porous hybrid inorganic/organic materialunder hydrothermal conditions in the presence of the pore restructuringtemplate. In a preferred embodiment, restructuring is made by fillingthe pores with the pore restructuring template. The pores are filled byadmixing the porous hybrid inorganic/organic material with an aqueousbase and the pore restructuring template. The base can be any Lewis baseincluding, for example, ammonium hydroxide, hydroxide salts of the groupI and group II metals, carbonate and hydrogencarbonate salts of thegroup I metals, or alkoxide salts of the group I and group II metals,and alkylamines (e.g., tris(hydroxymethyl)aminomethane,tetraethylammonium hydroxide). In a preferred embodiment, the base issodium hydroxide (NaOH).

The pore templating molecule works its way into the pores of the hybridmaterial via a hybrid silicate dissolution/precipitation process asexemplified in FIG. 2. At this point in the process, the pores of thehybrid material are filled with the ordered pore-templating micellebundles. The bundles restructure the pores into ordered domains.

To complete the pore restructuring process, the admixture of the poroushybrid inorganic/organic material, the aqueous mixture containing thebase and the pore templating molecule is heated at a temperature and fora period of time sufficient to form ordered domains. Typically, heatingtemperatures range from about 25 to about 200° C., more preferably 80 toabout 150° C., and most preferably from about 100 to about 130° C. Timeperiods for heating range from about 1 to about 120 hours, morepreferably 7 to about 120 hours, and most preferably from about 20 toabout 48 hours.

In the final step of the pore ordering process, the pore restructuringtemplate is removed. In one embodiment, removal is achieved byextraction using an acid wash. Acids that may be used includehydrochloric acid, hydrobromic acid, hydrofluoric acid, hydroiodic acid,sulfuric acid, formic acid, acetic acid, trichloroacetic acid,trifluoroacetic acid, or phosphoric acid. Water soluble solvents thatmay be used include acetonitrile, tetrahydrofuran, dimethylsulfoxide,dimethylformamide, methanol, ethanol, and isopropanol. In a preferredembodiment, a wash comprising concentrated hydrochloric acid and ethanolis used. The suspension of the material in the wash is heated to about25 to about 100° C., more preferably from 40 to about 60° C., and mostpreferably 50° C. for about 1 to about 30 hours, more preferably from 4to about 25 hours, and most preferably 20 hours.

In another embodiment, the pore restructuring template is removed bythermal treatment; i.e., by heating at a temperature ranging from about250 to about 600° C., more preferably from 275 to about 350° C., andmost preferably 300° C. for a period of time ranging from 1 to about 30hours, more preferably from 4 to about 25 hours, and most preferably 16hours. In a preferred embodiment, the as-processed material is placed ina suitable container, e.g., a stainless steel tube under a dynamic purgeof either air, nitrogen, and/or argon and heated to a temperature ofabout 250-550° C. for 16 hours after an initial hold at about 100° C.for 40 minutes.

In yet another embodiment, the pore restructuring template is removed byozonolysis treatment where the ozone degrades the surfactants into moreeasily removed by-products. See, e.g. T. Clark, Jr., J. D. Ruiz, H. Fan,C. J. Brinker, B. I. Swanson, A. N. Parikh Chem. Mater. 12 (2000) 3879and A. Gieldowska-Bulska, J. Perkowskil, and L. Kos Ozone: Science andEngineering, 26 (2004) 217.

In certain embodiments, porous hybrid inorganic/organic materialsalready possessing a chromatographically-enhancing pore geometry aresubjected to the pore restructuring process as described above to obtainporous hybrid inorganic/organic materials having achromatographically-enhancing pore geometry and comprising ordereddomains. In other embodiments, the pores of porous hybridinorganic/organic materials lacking a chromatographically-enhancing poregeometry are restructured as described above to obtain porous hybridinorganic/organic materials comprising a chromatographically-enhancingpore geometry as well as ordered domains. In other words, the porerestructuring process not only creates ordered domains but also createsa chromatographically-enhancing pore geometry. In still otherembodiments, porous hybrid inorganic/organic materials alreadypossessing a chromatographically-enhancing pore geometry are surfacemodified as described above followed by pore restructuring to providesurface modified porous hybrid inorganic/organic materials comprisingordered domains and having a chromatographically-enhancing poregeometry. These various embodiments are illustrated in Scheme 1 below.

EXAMPLES

The present invention may be further illustrated by the followingnon-limiting examples describing the preparation of porousinorganic/organic hybrid materials with ordered domains, and their use.

Materials

All reagents were used as received unless otherwise noted. Those skilledin the art will recognize that equivalents of the following supplies andsuppliers exist, and as such the suppliers listed below are not to beconstrued as limiting.

Characterization

Those skilled in the art will recognize that equivalents of thefollowing instruments and suppliers exist, and as such the instrumentslisted below are not to be construed as limiting.

Median macropore diameter (MPD) and macropore volume (MPV) were measuredby Mercury Porosimetry (Micromeritics AutoPore II 9220 or AutoPore IV,Micromeritics, Norcross, Ga.). The % C, % H, and % N values weremeasured by combustion analysis (CE-440 Elemental Analyzer; ExeterAnalytical Inc., North Chelmsford, Mass.). The specific surface areas(SSA), specific pore volumes (SPV) and the average pore diameters (APD)of these materials were measured using the multi-point N₂ sorptionmethod (Micromeritics ASAP 2400; Micromeritics Instruments Inc.,Norcross, Ga.). The specific surface area was calculated using the BETmethod, the specific pore volume was the single point value determinedfor P/P₀>0.98, and the average pore diameter was calculated from thedesorption leg of the isotherm using the BJH method. The microporesurface area (MPA), which is defined as the surface area in pores withdiameters less than or equal to 34 Å, was also determined from theadsorption leg of the isotherm using the BJH method. Particle sizes weremeasured using a Beckman Coulter Multisizer 3 analyzer (30-μm aperture,70,000 counts). The particle diameter (dp) was measured as the 50%cumulative volume diameter of the volume based particle sizedistribution. The width of the distribution was measured as the 90%cumulative volume diameter divided by the 10% cumulative volume diameter(90/10).

Example 1

Porous inorganic/organic hybrid particles comprising unbonded and C₁₈bonded particles were synthesized as described in U.S. Pat. No.6,686,035. The example from U.S. Pat. No. 6,686,035 which was followedto achieve the present material is indicated in Table 1 under theheading '035 Ref. Characterization data is listed in Table 1. Forexample 1e, the particle of type 1b was further modified withoctadecyltrichlorosilane as described in U.S. Pat. No. 6,686,035,Example 25.

TABLE 1 Composition of Hybrid Material '035 dp SSA SPV APD Product Priorto Modification Ref. (μm) 90/10 (m²/g) (cm³/g) (Å) 1aSiO₂/[C₂H₄(SiO_(1.5))₂]_(0.25) 3 4.76 1.47 191 0.78 151 1bSiO₂/(CH₃SiO_(1.5))_(0.5) 3 5.86 2.09 174 0.69 136 1cSiO₂/[C₂H₄(SiO_(1.5))₂]_(0.25) 2 4.09 5.13 602 0.78 47 1dSiO₂/[C₂H₄(SiO_(1.5))₂]_(0.25) 2 5.12 9.31 614 0.57 37 1eSiO₂/[C₂H₄(SiO_(1.5))₂]_(0.25)—(C₁₈) 25 4.79 1.48 119 0.49 126

Example 2

Porous unbonded hybrid inorganic/organic particles 1a and 1b having achromatographically-enhancing pore geometry were added to an aqueoussolution containing sodium hydroxide (Aldrich Chemical, Milwaukee, Wis.)and one or more of the following pore templating molecules (PTM):cetyltrimethylammonium bromide (C₁₆-TAB, Aldrich Chemical),trimethylstearylammonium chloride (C₁₈-TAC, TCI America, Portland,Oreg.), cetyltrimethylammonium chloride (C₁₆-TAC, 25 wt % in water,Aldrich Chemical); the following template swelling molecules (TSM):1,3,5-trimethylbenzene (TMB, Aldrich Chemical), yielding a suspension.The resultant suspension was mixed for 0.5 hours and was then enclosedin a stainless steel autoclave and heated to between 115° C. and 150° C.for 24-118 hours. After the autoclave cooled to room temperature theproduct was filtered and washed repeatedly using water and methanol(HPLC grade, J. T. Baker, Phillipsburgh, N.J.), and then dried at 80° C.under vacuum for 16 hours. Specific reagent amounts, reactionconditions, and characterization data are listed are listed in Table 2.

Example 3

Porous unbonded hybrid inorganic/organic particles 1c and 1d lacking achromatographically-enhancing pore geometry were added to an aqueoussolution containing sodium hydroxide (Aldrich Chemical, Milwaukee, Wis.)and one or more of the following pore templating molecules (PTM):cetyltrimethylammonium bromide (C₁₆-TAB, Aldrich Chemical),trimethylstearylammonium chloride (C₁₈-TAC, TCI America, Portland,Oreg.), cetyltrimethylammonium chloride (C₁₆-TAC, 25 wt % in water,Aldrich Chemical), Brij® 76 (Aldrich Chemical), Pluronic® P123 (AldrichChemical); and one or more of the following template swelling molecules(TSM): 1,3,5-trimethylbenzene (TMB, Aldrich Chemical),1,3,5-triisopropylbenzene (TIP, Aldrich Chemical) yielding a suspension.The resultant suspension was mixed for 0.5 hours and was then enclosedin a stainless steel autoclave and heated to between 115° C. and 150° C.for 24-118 hours. After the autoclave cooled to room temperature theproduct was filtered and washed repeatedly with water and then methanol(HPLC grade, J. T. Baker, Phillipsburgh, N.J.), and then dried at 80° C.under vacuum for 16 hours. Specific reagent amounts, reactionconditions, and characterization data are listed in Table 3.

Example 4

Octadecyltrichlorosilane C₁₈ bonded hybrid particles having achromatographically-enhancing pore geometry (1e) were added to anaqueous solution containing sodium hydroxide (Aldrich Chemical,Milwaukee, Wis.), anhydrous alcohol (HPLC grade, J. T. Baker,Phillipsburgh, N.J.), and one or more of the following pore templatingmolecules (PTM): cetyltrimethylammonium bromide (C₁₆-TAB, AldrichChemical), trimethylstearylammonium chloride (C₁₈-TAC, TCI America,Portland, Oreg.), cetyltrimethylammonium chloride (C₁₆-TAC, 25 wt % inwater, Aldrich Chemical), yielding a suspension. The resultantsuspension was mixed for 0.5 hours and was then enclosed in a stainlesssteel autoclave and heated to between 115° C. and 150° C. for 24-118hours. After the autoclave cooled to room temperature the product wasfiltered and washed repeatedly using water and then methanol (HPLCgrade, J. T. Baker), and then dried at 80° C. under vacuum for 16 hours.Specific reagent amounts, reaction conditions, and characterization dataare listed in Table 4.

TABLE 2 Pro- Particle Particle PTM Water NaOH TMB Temp Time SSA SPV APDMPV duct Reagent (g) PTM (g) (g) (g) (g) pH (° C.) (h) % C % H % N(m²/g) (cm³/g) (Å) (cm³/g) 2a 1a 15.0 C16-TAB 8.81 87.0 2.42 0 12.2 11524 16.99 3.38 0.59 224 0.81 125 — 2b 1a 15.0 C16-TAB 8.81 87.0 2.42 012.1 115 118 16.50 3.37 0.56 216 0.83 133 — 2c 1a 15.0 C18-TAC 8.41 87.02.42 0 13.0 150 24 19.48 3.86 0.55 148 0.77 175 — 2d 1a 15.0 C18-TAC8.41 87.0 2.42 13.0 12.7 115 24 20.63 4.12 0.70 — — — 0.61 2e 1b 15.0C16-TAC 7.69 86.5 2.40 0 11.6 115 24 17.80 3.86 0.60 104 0.55 151 — 2f1b 15.0 C18-TAC 8.36 86.5 2.40 13.0 12.5 115 24 24.36 5.15 0.87 118 0.3575 —

TABLE 3 Par- ticle Par- TSM Prod- Re- ticle PTM Water NaOH (mass, TempTime SSA SPV APD MPV uct agent (g) PTM (g) (g) (g) g) pH (° C.) (h) % C% H % N (m²/g) (cm³/g) (Å) (cm³/g) 3a 1c 15 C18-TAC 8.41 87.0 2.42 012.5 115 24 26.98 5.4 1.1 336 0.48 36 — 3b 1c 30 C18-TAC 8.41 87.0 4.830 12.6 115 24 24.0 4.77 0.89 — — — 0.41 3c 1c 15 C18-TAC 8.41 87.0 2.420 12.6 115 118 27.8 5.45 1.07 — — — 0.62 3d 1d 15 C18-TAC 8.41 87.0 2.420 12.8 115 24 26.93 5.30 0.99 — — — 0.23 3e 1d 15 C18-TAC 8.41 87.0 2.42TMB 12.8 115 24 27.77 5.43 1.17 — — — 0.31 (6.5) 3f 1d 15 C18-TAC 8.4187.0 2.42 TMB 12.8 115 24 27.69 5.46 1.16 — — — 0.34 (13.0) 3g 1d 15C18-TAC 8.41 87.0 2.42 TMB 12.4 115 24 26.95 5.37 1.09 — — — 0.32 (6.5)3h 1d 15 C18-TAC 8.41 87.0 2.42 TMB 12.7 115 24 28.63 5.67 1.13 — — —0.33 (13.0) 3i 1d 15 C18-TAC 8.41 87.0 2.42 TMB 12.7 115 24 28.25 5.631.03 — — — 0.43 (18.0) 3j 1d 15 C18-TAC 8.41 87.0 2.42 TMB 12.7 115 2428.38 5.69 1.01 — — — 0.34 (6.5), TIB (6.5) 3k 1d 15 C18-TAC 8.41 87.02.42 TIB 12.8 115 24 29.32 5.72 1.02 — — — 0.27 (12.9) 3l 1d 15 Brij-766.49 89.3 1.13 0 12.6 115 24 8.94 1.94 0.00 — — — 0.61 3m 1d 7 Pluronic5.10 89.0 1.13 0 12.2 115 24 7.60 1.62 0.00 — — — 0.63 P123 3n 1d 15C18-TAC 8.41 87.0 2.42 TMB 12.6 115 24 26.17. 5.25 1.01 — — — 0.42(13.0) 3o 1d 15 C18-TAC 8.41 87.0 2.42 TMB 12.1 115 24 27.66 5.42 1.10 —— — 0.32 (13.0)) 3p 1d 15 C18-TAC 8.41 87.0 2.42 TMB 11.3 115 24 27.545.37 1.08 — — — 0.34 (13.0) 3q 1d 5.2 C18-TAC 2.91 30.2 0.84 TMB 12.9115 24 23.95 4.76 0.86 — — — 0.16 (6.2)

TABLE 4 Particle Particle PTM Water Alcohol NaOH Temp SSA SPV APDProduct Reagent (g) PTM (g) (g) (g) (g) pH (° C.) % C % H % N (m²/g)(cm³/g) (Å) 4a 1e 15 C18-TAC 8.41 86.96 0 2.42 12.9 150 27.24 5.15 0.47101 0.54 174 4b 1e 15 C18-TAC 8.41 86.96 22.6 2.42 12.7 150 24.95 4.740.23 72 0.62 266

Example 5

Selected samples of hybrid material prepared according to Examples 2, 3,and 4 were mixed in a solution containing the following: anhydrousethanol (HPLC grade, J. T. Baker, Phillipsburgh, N.J.) and concentratedhydrochloric acid (Aldrich Chemical, Milwaukee, Wis.), and stirred in a5 L round bottom flask. The suspension was then heated to 50° C. for 20hours. After the reaction cooled to room temperature the product wasfiltered and washed repeatedly with water. This reaction was thenrepeated (50° C., 20 hours). Final product was washed with acetone andthen dried at 80° C. under reduced pressure for 16 hours. Specificreagent amounts, reaction conditions, and characterization data arelisted in Table 5. The XRPD plot for Example 5e is shown in FIG. 3, anda peak maximum is listed in table 9.

Example 6

Selected samples of hybrid materials prepared according to Examples 2and 3 were heated in a furnace (Model F6000, Barnstead/Thermolyne,Dubuque, Iowa) or within a stainless steel tube (19×50 mm) under adynamic purge of either air or argon at 250-550° C. for 16 hours, afteran initial hold at 100° C. for 40 minutes. Specific reaction conditionsand characterization data are listed in Table 6. Selected materials weretested by XRPD, and peak maxima are listed in table 9. Exemplary plotsfor Examples 6r and 61 are shown in FIG. 3. An exemplary plot of Example6t is shown in FIG. 4.

TABLE 5 Particle Particle HCl Alcohol SSA SPV APD MPA Product Reagent(g) (g) (L) % C % H % N (m²/g) (cm³/g) (Å) (m²/g) 5a 2a 8.6 24.1 1.297.97 1.66 0.00 374 1.06 112 96 5b 2b 10.0 28.0 1.50 7.68 1.74 0.00 3441.09 118 94 5c 2e 10.0 28.0 1.50 8.00 2.1 0.00 421 1.22 156 105 5d 3a10.0 28.0 1.50 8.27 1.79 0.00 710 1.11 41 28 5e 3b 23 64.4 3.45 8.371.81 0.00 552 1.01 55 19 5f 3c 7.0 19.6 1.05 8.73 1.96 0.05 670 1.09 4256 5g 4b 9.0 25.2 1.35 21.09 3.95 0.00 102 0.74 257 12 5h 2c 5.0 14.00.75 7.79 1.72 0.03 296 1.08 132 73

TABLE 6 Product Particle Particle Gas Method Temp Product % C % H % NSSA SPV APD MPA 6a 2c 1.00 air oven 250 0.70 8.24 1.40 0.00 292 1.04 14162 6b 2c 1.00 air oven 350 0.60 5.73 1.18 0.00 300 1.08 138 40 6c 2c1.00 air oven 550 0.90 0.61 0.15 0.00 254 0.93 138 67 6d 2c 1.00 argonoven 250 0.80 8.58 1.47 0.00 283 1.04 144 54 6e 2c 1.00 argon tube 2750.70 8.54 1.74 0.00 292 1.07 135 76 6f 2c 1.00 argon tube 375 0.70 8.201.54 0.00 299 1.07 132 78 6g 2d 1.14 argon tube 275 0.81 8.66 1.71 0.00390 0.99 96 75 6h 3b 1.17 argon tube 275 0.84 9.66 1.87 0.00 500 0.93 5489 6i 3d 1.40 argon tube 275 0.90 10.04 1.88 0.00 636 0.76 36 442 6j 3f1.40 argon tube 275 0.95 9.97 1.96 0.00 542 0.93 57 40 6k 3h 1.51 argontube 300 0.95 9.73 1.91 0.00 635 0.93 48 108 6l 3g 1.47 argon tube 3001.03 9.85 1.89 0.00 601 0.88 45 70 6m 3i 2.15 argon tube 300 1.50 9.631.92 0.00 600 1.02 56 57 6n 3j 2.41 argon tube 300 1.67 9.96 1.83 0.00575 0.99 50 25 6o 3k 2.43 argon tube 300 1.63 9.72 1.77 0.00 608 0.88 4552 6p 3l 1.51 argon tube 300 1.36 8.29 1.59 0.00 243 0.77 119 31 6q 3m1.60 argon tube 300 1.24 7.56 1.46 0.00 242 0.75 122 29 6r 3f 4.64 argontube 300 3.35 10.24 1.93 0.00 537 0.93 57 34 6s 3n 2.20 argon tube 3001.46 9.54 1.79 0.00 572 0.98 59 43 6t 3o 2.52 argon tube 300 1.34 9.981.87 0.00 561 0.94 50 23 6u 3p 2.56 argon tube 300 1.73 9.99 1.85 0.00576 0.93 48 21 6v 3q 2.43 argon tube 300 1.70 9.30 1.88 0.00 422 0.56 4851

Example 7

The particles of example 5 g were suspended in hexamethyldisilazane(HMDS, Aldrich Chemical, Milwaukee, Wis.). The suspension was thentransferred to a glass lined stainless steel autoclave and heated at200° C. for 20 hours, under a static argon blanket. After the autoclavecooled to room temperature the product was filtered and washedrepeatedly using toluene, acetone/water, and acetone, and then dried at80° C. under vacuum for 16 hours. % C and % H data are listed in Table7.

TABLE 7 Particle Particle Product Reagent (g) % C % H 7a 5 g 7 17.373.39

Example 8

A porous inorganic/organic hybrid monolith was synthesized by thefollowing procedure. A non-ionic surfactant, Pluronic® P105 (15.9 g,Aldrich Chemical) was dissolved in 100 mL of 0.09 M acetic acid (J. T.Baker) and chilled to 0° C. To this solution was added a mixture of1,2-bis-(trimethoxysilyl)ethane (5.8 mL, Gelest Inc., Morrisville, Pa.)and tetramethoxysilane (34.2 mL, Aldrich Chemical). The resultingsolution was stirred at 0° C. for 1.5 h and then aliquots weretransferred to glass vials, sealed, and kept at 45° C. for 2 days. Thesolution solidified, and a white rod was produced, which was thenimmersed into a 0.1 M ammonium hydroxide (J. T. Baker) water solution at60° C. for 16 hours. The resultant rods were washed by immersing inrefluxing water for 3 h, cooling, replacing the water, and repeating asecond three hours. A second wash cycle was repeated using methanol(HPLC grade, J. T. Baker). Selected rods were vacuum dried at 80° C. for16 h. Characterization data is listed in Table 8.

TABLE 8 Composition of Hybrid Material MPD MPV SSA SPV APD Product Priorto Modification (μm) (cm³/g) (m²/g) (cm³/g) (Å) 8aSiO₂/[C₂H₄(SiO_(1.5))₂]_(0.1) 12.6 2.70 693 1.47 69

To achieve a porous hybrid inorganic/organic monolith comprising ordereddomains and having a chromatographically-enhancing pore geometry, amonolith of type 8a would be immersed in an aqueous solution containingsodium hydroxide (Aldrich Chemical, Milwaukee, Wis.) and one or more ofthe following pore templating molecules (PTM): cetyltrimethylammoniumbromide (C₁₆-TAB, Aldrich Chemical), trimethylstearylammonium chloride(C₁₈-TAC, TCI America, Portland, Oreg.), cetyltrimethylammonium chloride(C₁₆-TAC, 25 wt % in water, Aldrich Chemical), Brij® 76 (AldrichChemical), Pluronic® P123 (Aldrich Chemical); and one or more of thefollowing template swelling molecules (TSM): 1,3,5-trimethylbenzene(TMB, Aldrich Chemical), 1,3,5-triisopropylbenzene (TIP, AldrichChemical). The suspended monolith would be immersed for 0.5 hours andwas then enclosed in a stainless steel autoclave and heated to between115° C. and 150° C. for 24-118 hours. After the autoclave cooled to roomtemperature, the monolith would be removed and washed repeatedly asdescribed above with water and then methanol, and then dried at 80° C.under vacuum for 16 hours.

Example 9

XRPD data were collected using two methods (A and B) as described below.Peak maxima for selected materials are listed in Table 9.

Method A data were collected by SSCI Incorporated, West Lafayette, Ind.Sample Preparation Specimens were very firmly packed into a depressionin a silicon zero-background holder (ZBH) mounted on aluminum. Thespecimen surfaces were very carefully leveled by pressing a smooth,glass slide onto the specimen until the specimen surface was flush withthe top surface of the ZBH. The surface of the specimen and ZBH wasexamined with an optical microscope and a flat edge to check forflatness and flushness. Technique: NIST SRM 649C Si powder, d-spacecalibrant was measured as an external standard. The XPRD patterns werecollected with a Shimadzu XRD-6000 using the following instrumentalparameters. Radiation: long, fine focus; Anode: Cu; Power: 40 kV and 40mA; 2θ Range: 1.0° to 10° 2θ or 0.8° to 50° 2θ; Step 0.04° 2θ; ScanSpeed: 0.6° 2θ/minute; Divergence slit: 0.5°; Anti-scatter slits: 0.5°;receiving slits: 0.15 mm; Detector: NaI scintillation counter;Diffracted-beam monochrometer: graphite. The diffractogram plots werenot smoothed, and no background subtraction was employed. Diffractionpeak maxima were determined manually from the diffractogram plot.Diffraction peaks were broad, approximately 1° 2θ.

Method B data were collected by H&M Analytical Services, Inc.,Allentown, N.J. All diffraction scans were run on a Siemens D5000 Θ/Θdiffractometer in a Bragg-Brentano parafocusing geometry and using Curadiation at 40 KV/30 mA from a long fine focus tube. Scans were runover the angular range of 1° to 6° with a step size of 0.05° andcounting times of 300 to 600 seconds per step. To reduce the angulardivergence and reduce the background, narrow slits were used (divergenceslit=0.1 mm, anti-scatter slit=0.2 mm, detector slit=0.1 mm). Underthese conditions, the angular divergence of the instrument isapproximately 0.05°. Since the individual diffraction peaks were in theneighborhood of 0.4° to 0.5°, the chosen step size provided 8-10 datapoints within the FWHM, which is adequate for determining the peakpositions. Two types of scans were run. The first consisted of the testsample, which was deposited onto a zero background holder and thinned toa layer thickness of approximately 50 μm by use of a methanol slurry.This method has the added advantage of producing a very smooth surface,which is desirable for low angle work. The second type of test consistedof the test sample mixed with a small amount of Silver Behenate(C₂₂H₄₄O₂Ag produced by Kodak and described in Powder Diffraction, 10,91-95 (1995)). Silver Behenate is an ideal low-angle standard due to itsvery large lattice parameter that produces a series of diffraction linesat angles as low as 1.513°. To perform the internal calibration usingSilver Behenate, the pattern containing the internal standard was firstmodified to bring the Silver Behenate peaks into their calibratedpositions. Once this was done, the unspiked sample was then corrected tobring it into coincidence with the features of the standard pattern thatare common to both patterns. This indirect method of internalcalibration had to be used since the strongest peak from the standardand the strongest peak from the test material overlapped. Although thisindirect method is not as accurate as the conventional internal standardmethod, the accuracy is still deemed to be quite good, with an expectederror of approximately 0.02°, which is about ten times better than theuncorrected pattern. All patterns were analyzed with the use of thecommercial program Jade v6.5 (produced by Materials Data Inc.). Eachpattern was corrected for systematic errors by use of the internalstandard. The background was then fitted with a parabolic fittingfunction and stripped. There was no reason to remove the Kα₂ peakartifact, since it is so close to the Kα₁ peak at these low angles thatthey are indistinguishable. Once the background was removed, the peakpositions were then determined by a centroid fitting function. Thesepositions were then refined with the aid of a least squares process thatfits the individual peaks to a split Pearson VII function.

TABLE 9 XRPD XRPD Peak Maxima Product Method (°2θ) 5e A 1.3 6i A 1.5,3.2 6j A 1.5, 2.5 6l A 1.5, 2.5, 3.2 6m A 1.5, 2.5 6n A 1.5, 2.5 6o A1.5, 2.5 6r A 1.5, 2.5 6s A 1.5, 2.5 6t A 1.5, 2.5 B 1.9, 2.6 6u A 1.5,2.5 6v A 1.5, 2.5, 3.2

Example 10

FIG. 5 shows a transmission electron micrograph of compounds A and B.Compound A, a porous inorganic/organic hybrid material having ordereddomains, is prepared as described in Example 6. Compound B is aninorganic material (silica gel) with ordered domains. Compounds A and Bwere examined using transmission electron microscopy (TEM). Themicrograph of FIG. 5 shows patterns that are characteristic of materialshaving ordered domains.

INCORPORATION BY REFERENCE

The entire contents of all patents, published patent applications andother references cited herein are hereby expressly incorporated hereinin their entireties by reference.

EQUIVALENTS

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, numerous equivalents to thespecific procedures described herein. Such equivalents were consideredto be within the scope of this invention and are covered by thefollowing claims. The contents of all references, issued patents, andpublished patent applications cited throughout this application arehereby incorporated by reference.

1. A porous hybrid inorganic/organic material comprising ordered domains and having a chromatographically-enhancing pore geometry.
 2. A porous hybrid inorganic/organic material comprising ordered domains having formula I, II or III below: (A)_(x)(B)_(y)(C)_(z)  (Formula I) wherein the order of repeat units A, B, and C may be random, block, or a combination of random and block; A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond; B is an organosiloxane repeat unit which is bonded to one or more repeat units B or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond; C is an inorganic repeat unit which is bonded to one or more repeat units B or C via an inorganic bond; and x, y are positive numbers and z is a non negative number, wherein when z=0, then 0.002≦x/y≦210, and when z≠0, then 0.0003≦y/z≦500 and 0.002≦z/(y+z)≦210; (A)_(x)(B)_(y)(B*)_(y*)(C)_(z)  (Formula II) wherein the order of repeat units A, B, B*, and C may be random, block, or a combination of random and block; A is an organic repeat unit which is covalently bonded to one or more repeat units A or B via an organic bond; B is an organosiloxane repeat units which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond and which may be further bonded to one or more repeat units A or B via an organic bond; B* is an organosiloxane repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic siloxane bond, wherein B* is an organosiloxane repeat unit that does not have reactive (i.e., polymerizable) organic components and may further have a protected functional group that may be deprotected after polymerization; C is an inorganic repeat unit which is bonded to one or more repeat units B or B* or C via an inorganic bond; and x, y are positive numbers and z is a non negative number, wherein when z=0, then 0.002≦x/(y+y*)≦210, and when z≠0, then 0.0003≦(y+y*)/z≦00 and 0.002≦x/(y+y*+z)≦210; or [A]_(y)[B]_(x)  (Formula III), wherein x and y are whole number integers and A is SiO₂/(R¹ _(p)R² _(q)SiO_(t))_(n) or SiO₂/[R³(R¹ _(r)SiO_(t))_(m)]_(n); wherein R¹ and R² are independently a substituted or unsubstituted C₁ to C₇ alkyl group, or a substituted or unsubstituted aryl group, R³ is a substituted or unsubstituted C₁ to C₇ alkylene, alkenylene, alkynylene, or arylene group bridging two or more silicon atoms, p and q are 0, 1, or 2, provided that p+q=1 or 2, and that when p+q=1, t=1.5, and when p+q=2, t=1; r is 0 or 1, provided that when r=0, t=1.5, and when r=1, t=1; m is an integer greater than or equal to 2; and n is a number from 0.01 to 100; B is: SiO₂/(R⁴ _(v)SiO_(t))_(n) wherein R⁴ is hydroxyl, fluorine, alkoxy, aryloxy, substituted siloxane, protein, peptide, carbohydrate, nucleic acid, or combinations thereof, R⁴ is not R¹, R², or R³; v is 1 or 2, provided that when v=1, t=1.5, and when v=2, t=1; and n is a number from 0.01 to 100; wherein the material of formula III has an interior area and an exterior surface, and said interior area of said material has a composition represented by A; said exterior surface of said material has a composition represented by A and B, and wherein said exterior composition is between about 1 and about 99% of the composition of B and the remainder comprising A.
 3. The hybrid material of claim 1, wherein diffraction peak maxima observed for said material exhibit a 2θ position that excludes diffraction peaks resulting from atomic-range order that are associated with amorphous material.
 4. The hybrid material of claim 3, wherein the excluded diffraction peak ranges from about 20° to about 23° 2θ.
 5. The hybrid material of claim 1, wherein said inorganic portion of said hybrid material is selected from the group consisting of alumina, silica, titanium or zirconium oxides, and ceramic materials.
 6. The hybrid material of claim 5 wherein said inorganic portion of said hybrid material is silica.
 7. The hybrid material of claim 1, wherein the percentage by mass of ordered domains of said material ranges from about 1% to about 100%.
 8. The hybrid material of claim 1, wherein pores of a diameter of less than about 34 Å contribute less than about 110 m²/g to less than about 50 m²/g to the specific surface area of the material.
 9. The hybrid material of claim 1 or, wherein said material comprises porous inorganic/organic hybrid particles.
 10. The hybrid material of claim 1, wherein said material comprises a monolith.
 11. The hybrid material of claim 10, wherein said monolith comprises coalesced porous inorganic/organic hybrid particles.
 12. The hybrid material of claim 9, wherein said particles are essentially spherical.
 13. The hybrid material of claim 9, wherein said particles have a specific surface area of about 50 to 800 m²/g, said particles have specific pore volumes of about 0.25 to 1.5 cm³/g, and said particles have an average pore diameter of about 50 to 500 Å.
 14. The hybrid material of claim 13, wherein said particles have a specific surface area of about 100 to 700 m²/g.
 15. The hybrid material of claim 13, wherein said particles have a specific surface area of about 300 to 600 m²/g.
 16. The hybrid material of claim 13, wherein said particles have specific pore volumes of about 0.7 to 1.3 cm³/g.
 17. The hybrid material of claim 13, wherein said particles have an average pore diameter of about 50 to 300 Å.
 18. The hybrid material of claim 1, wherein said material comprises porous hybrid inorganic/organic particles that have a micropore surface area of less than about 110 m²/g.
 19. The hybrid material of claim 18, wherein said particles have a micropore surface area of less than about 105 m²/g.
 20. The hybrid material of claim 18, wherein said particles have a micropore surface area of less than about 80 m²/g.
 21. The hybrid material of claim 18, wherein said particles have a micropore surface area of less than about 50 m²/g.
 22. The hybrid material of claim 9, wherein said particles have been surface modified by a surface modifier selected from the group consisting of an organic group surface modifier, a silanol group surface modifier, a polymeric coating surface modifier, and combinations thereof.
 23. The hybrid material of claim 22, wherein said hybrid particles have been surface modified with a surface modifier having the formula Z_(a)(R′)_(b)Si—R, where Z=Cl, Br, I, C₁-C₅ alkoxy, dialkylamino or trifluoromethanesulfonate; a and b are each an integer from 0 to 3 provided that a+b=3; R′ is a C₁-C₆ straight, cyclic or branched alkyl group, and R is a functionalizing group.
 24. The hybrid material of claim 23, wherein R′ is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, sec-butyl, pentyl, isopentyl, hexyl and cyclohexyl.
 25. The hybrid material of claim 23, wherein the functionalizing group R is selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, cyano, amino, diol, nitro, ester, a cation or anion exchange group, or an alkyl or aryl group containing an embedded polar functionality.
 26. The hybrid material of claim 25, wherein said functionalizing group R is a C₁-C₃₀ alkyl group.
 27. The hybrid material of claim 25, wherein said functionalizing group R is a C₁-C₂₀ alkyl group.
 28. The hybrid material of claim 22, wherein said surface modifier is selected from the group consisting of octyltrichlorosilane, octadecyltrichlorosilane, octyldimethylchlorosilane, and octadecyldimethylchlorosilane.
 29. The hybrid material of claim 28, wherein said surface modifier is octyltrichlorosilane or octadecyltrichlorosilane.
 30. The hybrid material of claim 22, wherein said particles have been surface modified by coating with a polymer.
 31. The hybrid material of claim 22, wherein said particles have been surface modified by a combination of an organic group surface modifier and a silanol group surface modifier.
 32. The hybrid material of claim 22, wherein said particles have been surface modified by a combination of an organic group surface modifier and a polymeric coating surface modifier.
 33. The hybrid material of claim 22, wherein said particles have been surface modified by a combination of a silanol group surface modifier and a polymeric coating surface modifier.
 34. The hybrid material of claim 22, wherein said particles have been surface modified via formation of an organic covalent bond between an organic group of the particle and a surface modifier.
 35. The hybrid material of claim 22, wherein said particles have been surface modified by a combination of an organic group surface modifier, a silanol group surface modifier, and a polymeric coating surface modifier.
 36. The hybrid material of claim 22, wherein said particles have been surface modified by a silanol group surface modifier.
 37. The hybrid material of claim 1 having the formula SiO₂/(R² _(p)R⁴ _(q)SiO_(t))_(n) or SiO₂/[R⁶(R² _(r)SiO_(t))_(m)]_(n) wherein R² and R⁴ are independently C₁-C₁₈ aliphatic or aromatic moieties optionally substituted with alkyl, aryl, cyano, amino, hydroxyl, diol, nitro, ester, ion exchange or embedded polar functionalities, R⁶ is a substituted or unsubstituted C₁-C₁₈ alkylene, alkenylene, alkynylene or arylene moiety bridging two or more silicon atoms, p and q are 0, 1 or 2, provided that p+q=1 or 2, and that when p+q=1, t=1.5, and when p+q=2, t=1; r is 0 or 1, provided that when r=0, t=1.5, and when r=1, t=1; m is an integer greater than or equal to 2, and n is a number from 0.03 to 1.5.
 38. The hybrid material of claim 37, wherein n is a number from 0.1 to 1.0.
 39. The hybrid material of claim 37, wherein n is a number from 0.2 to 0.5.
 40. The hybrid material of Formula II according to claim 2, wherein B is bonded to one or more repeat units B or C via an inorganic siloxane bond and is bonded to one or more repeat units A or B via an organic bond.
 41. The hybrid material of Formula I or II according to claim 2, wherein 0.003≦y/z≦50 and 0.02≦x/(y+z)≦21.
 42. The hybrid material of Formula I or II according to claim 2, wherein 0.03≦y/z≦5 and 0.2≦x/(y+z)≦2.1.
 43. The hybrid material of Formula I or II according to claim 2, wherein A is a substituted ethylene group, B is a oxysilyl-substituted alkylene group, and C is a oxysilyl group.
 44. The hybrid material of Formula I or II according to claim 2, wherein A is selected from the group consisting of

wherein each R is independently H or a C₁-C₁₀ alkyl group; m is an integer of from 1 to 20; n is an integer of from 0 to 10; and Q is hydrogen, N(C₁₋₆alkyl)₃, N(C₁₋₆alkyl)₂(C₁₋₆alkylene-SO₃), or C(C₁₋₆hydroxyalkyl)₃.
 45. The hybrid material according to claim 44, wherein each R is independently hydrogen, methyl, ethyl, or propyl.
 46. The hybrid material of Formula I or II according to claim 2, wherein B is selected from the group consisting of

and wherein B* is selected from a group consisting of


47. The hybrid material of Formula I or II according to claim 2, wherein C is


48. The hybrid material of Formula III of claim 2, wherein said exterior surface has a composition that is between about 50 and about 90% of composition B, with the remainder comprising composition A.
 49. The hybrid material of claim 48 wherein said exterior surface has a composition that is between about 70 and about 90% of composition B, with the remainder comprising composition A.
 50. The hybrid material of Formula III of claim 2, wherein R⁴ is hydroxyl.
 51. The hybrid material of Formula III of claim 2, wherein R⁴ is fluorine.
 52. The hybrid material of Formula III of claim 2, wherein R⁴ is methoxy.
 53. The hybrid material of Formula III of claim 2, wherein R⁴ is —OSi(R⁵)₂—R⁶ wherein R⁵ is a C₁ to C₆ straight, cyclic, or branched alkyl, aryl, or alkoxy group, a hydroxyl group, or a siloxane group, and R⁶ is a C₁ to C₃₆ straight, cyclic, or branched alkyl, aryl, or alkoxy group, wherein R⁶ is unsubstituted or substituted with one or more moieties selected from the group consisting of halogen, cyano, amino, diol, nitro, ether, carbonyl, epoxide, sulfonyl, cation exchanger, anion exchanger, carbamate, amide, urea, peptide, protein, carbohydrate, nucleic acid functionalities, and combinations thereof.
 54. The hybrid material of claim 53, wherein R⁶ is a C₁₈ group.
 55. The material of claim 53, wherein R⁶ is a cyanopropyl group.
 56. A method of preparing a porous hybrid inorganic/organic material comprising ordered domains of claim 1, comprising the steps of: (a) forming a pore restructuring template; (b) restructuring the pores of a porous hybrid inorganic/organic material by contacting the pores of the porous hybrid inorganic/organic material with the pore restructuring template, to thereby restructure the pores into ordered domains; and (c) removing the pore restructuring template from the restructured pores; to thereby prepare a porous hybrid inorganic/organic material comprising ordered domains.
 57. The method of claim 56, wherein the restructuring of step (b) comprises admixing the porous hybrid inorganic/organic material with an aqueous solution containing a base and a pore restructuring template, and heating the admixture at a temperature and for a period of time sufficient to form ordered domains. 58-79. (canceled)
 80. The method of claim 56, further comprising modifying the pore structure of the porous hybrid inorganic/organic material to thereby form a chromatographically-enhancing pore geometry, to thereby prepare a porous hybrid inorganic/organic material comprising ordered domains and having a chromatographically-enhancing pore geometry. 81-97. (canceled)
 98. A separations device comprising a porous hybrid inorganic/organic hybrid material of claim
 1. 99. A separations device of claim 98 selected from the group consisting of chromatographic columns, thin layer chromatographic (TLC) plates, filtration membranes, microtiter plates, scavenger resins, and solid phase organic synthesis supports.
 100. A chromatographic column comprising a) a column having a cylindrical interior for accepting porous hybrid inorganic/organic material, and b) a chromatographic bed comprising a porous hybrid inorganic/organic material of claim
 1. 101. A porous hybrid inorganic/organic material of claim 1, prepared by a process comprising the steps of: (a) forming a pore restructuring template; (b) restructuring the pores of a porous hybrid inorganic/organic material by contacting the pores of the porous hybrid inorganic/organic material with the pore restructuring template, to thereby restructure the pores into ordered domains; and (c) removing the pore restructuring template from the restructured pores.
 102. The hybrid material of claim 101, wherein the restructuring of step (b) comprises admixing the porous hybrid inorganic/organic material with an aqueous solution containing a base and a pore restructuring template, and heating the admixture at a temperature and for a period of time sufficient to form ordered domains. 103-115. (canceled)
 116. The hybrid material of claim 101, wherein the process further comprises modifying the pore structure of the porous hybrid inorganic/organic material to thereby form a chromatographically-enhancing pore geometry, to thereby prepare a porous hybrid inorganic/organic material comprising ordered domains and having a chromatographically-enhancing pore geometry. 117-133. (canceled) 